Mixed decyl mercaptans compositions and use thereof as mining chemical collectors

ABSTRACT

Disclosed herein is a process for the recovery of a metal from an ore using a collector composition. The process includes contacting the ore with the collector composition. The collector composition can include sulfur-containing compounds comprising (i) mercaptans comprising branched C 10  mercaptans compounds selected from the group consisting of 5-methyl-1-mercapto-nonane, 3-propyl-1-mercapto-heptane, 4-ethyl-1-mercapto-octane, 2-butyl-1-mercapto-hexane, 5-methyl-2-mercapto-nonane, 3-propyl-2-mercapto-heptane, 4-ethyl-2-mercapto-octane, 5-methyl-5-mercapto-nonane, and combinations thereof; and (ii) sulfides comprising branched C 20  sulfides represented by the structure R 1 —S—R 2 , wherein R 1  and R 2  are each independently a functional group derived from an olefin, wherein the olefin comprises 5-methyl-1-nonene, 3-propyl-1-heptene, 4-ethyl-1-octene, 2-butyl-1-hexene, or combinations thereof.

TECHNICAL FIELD

The present disclosure relates to compositions containing mixed decylmercaptans and/or mixed decyl sulfides and use thereof in miningcollector compositions. More specifically, the present disclosurerelates to compositions containing branched decyl mercaptans and/orbranched C₂₀ sulfides, and methods of making same.

BACKGROUND

Mercaptans, which are also known as thiols, are organic compounds usedin diverse applications. Some mercaptans can be used as precursors foragriculture chemicals or as natural gas additives. While processes formaking mercaptans are available, preparing individual mercaptans can becostly due to numerous purification steps required for the feedstockand/or mercaptan product. However, many applications may not require asingle pure mercaptan compound, but could utilize mercaptan mixtures.Thus, there is a need to develop mercaptan compositions suitable forsuch applications, and methods of making same.

One such application is the extraction and recovery of metals from minedores. In the past, mercaptans such as n-dodecyl mercaptans (NDDM) andtert-dodecyl mercaptans (TDDM) have been used as mining chemicalcollectors in the extraction and recovery of metals from mined ore.However, NDDM and TDDM have fallen out of favor in the mining industrydue to strong odors. Thus, there is an ongoing need for mining chemicalcollector compositions suitable for metals recovery from mined ore.

BRIEF SUMMARY

Disclosed herein is a process for the recovery of a metal from an ore,the process comprising contacting the ore with a collector composition,wherein the collector composition comprises sulfur-containing compounds,wherein the sulfur-containing compounds comprise (i) mercaptanscomprising branched C₁₀ mercaptans compounds selected from the groupconsisting of 5-methyl-1-mercapto-nonane, 3-propyl-1-mercapto-heptane,4-ethyl-1-mercapto-octane, 2-butyl-1-mercapto-hexane,5-methyl-2-mercapto-nonane, 3-propyl-2-mercapto-heptane,4-ethyl-2-mercapto-octane, 5-methyl-5-mercapto-nonane, and combinationsthereof; and (ii) sulfides comprising branched C₂₀ sulfides representedby the structure R¹—S—R², wherein R¹ and R² are each independently afunctional group derived from an olefin, wherein the olefin comprises5-methyl-1-nonene, 3-propyl-1-heptene, 4-ethyl-1-octene,2-butyl-1-hexene, or combinations thereof.

Also disclosed herein is a collector composition comprisingsulfur-containing compounds. The sulfur-containing compounds comprise(i) mercaptans comprising branched C₁₀ mercaptans compounds selectedfrom the group consisting of 5-methyl-1-mercapto-nonane,3-propyl-1-mercapto-heptane, 4-ethyl-1-mercapto-octane,2-butyl-1-mercapto-hexane, 5-methyl-2-mercapto-nonane,3-propyl-2-mercapto-heptane, 4-ethyl-2-mercapto-octane,5-methyl-5-mercapto-nonane, and combinations thereof; and (ii) sulfidescomprising branched C₂₀ sulfides represented by the structure R¹—S—R²,wherein R¹ and R² are each independently a functional group derived froman olefin, wherein the olefin comprises 5-methyl-1-nonene,3-propyl-1-heptene, 4-ethyl-1-octene, 2-butyl-1-hexene, or combinationsthereof.

BRIEF DESCRIPTION OF THE DRAWINGS

For a detailed description of the preferred embodiments of the disclosedcompositions and methods of making same, reference will now be made tothe accompanying drawings in which:

FIG. 1 displays a reaction schematic for addition of hydrogen sulfide(H₂S) to an olefin;

FIG. 2 displays a GC trace of a crude product from an UV initiatedreaction after removal of residual H₂S;

FIG. 3 displays a GC trace of a reaction product from an UV initiatedreaction after removal of lights;

FIG. 4 displays a GC trace of a crude product from an UV initiatedreaction after removal of residual H₂S;

FIG. 5 displays a GC trace of a reaction product from an UV initiatedreaction after removal of lights;

FIG. 6 displays a comparison of GC traces for a product obtained by UVinitiation and a product obtained by acid catalysis. The upperchromatogram is the UV-initiated C₁₀ mercaptan product, and the lowerchromatogram is the acid catalyzed C₁₀ mercaptan product;

FIG. 7 displays a comparison of GC traces for a C₁₀ mercaptan fractionisolated from a product obtained by UV initiation and a C₁₀ mercaptanfraction isolated from a product obtained by acid catalysis, andparticularly, representative GC profiles of the purified C₁₀ mercaptanreaction product. The upper chromatogram is the acid catalyzed C₁₀mercaptan product, and the lower chromatogram is the UV-initiated C₁₀mercaptan product; and

FIG. 8 displays a GC trace of a crude product from a reaction catalyzedby a hydrodesulfurization catalyst after removal of residual H₂S.

DETAILED DESCRIPTION

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure, butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2^(nd) Ed (1997) can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied. To the extent that any definitionor usage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

Groups of elements of the Periodic Table are indicated using thenumbering scheme indicated in the version of the Periodic Table ofelements published in Chemical and Engineering News, 63(5), 27, 1985. Insome instances, a group of elements can be indicated using a common nameassigned to the group; for example, alkali metals for Group 1 elements,alkaline earth metals (or alkaline metals) for Group 2 elements,transition metals for Groups 3-12 elements, and halogens for Group 17elements.

Regarding claim transitional terms or phrases, the transitional term“comprising”, which is synonymous with “including,” “containing,”“having,” or “characterized by,” is inclusive or open-ended and does notexclude additional, unrecited elements or method steps. The transitionalphrase “consisting of” excludes any element, step, or ingredient notspecified in the claim. The transitional phrase “consisting essentiallyof” limits the scope of a claim to the specified materials or steps andthose that do not materially affect the basic and novelcharacteristic(s) of the claimed invention. The term “consistingessentially of” occupies a middle ground between closed terms like“consisting of” and fully open terms like “comprising.” Absent anindication to the contrary, when describing a compound or composition,“consisting essentially of” is not to be construed as “comprising,” butis intended to describe the recited component that includes materialswhich do not significantly alter the composition or method to which theterm is applied. For example, a feedstock consisting essentially of amaterial A can include impurities typically present in a commerciallyproduced or commercially available sample of the recited compound orcomposition. When a claim includes different features and/or featureclasses (for example, a method step, feedstock features, and/or productfeatures, among other possibilities), the transitional terms comprising,consisting essentially of, and consisting of apply only to the featureclass to which is utilized and it is possible to have differenttransitional terms or phrases utilized with different features within aclaim. For example, a method can comprise several recited steps (andother non-recited steps), but utilize a catalyst system preparationconsisting of specific steps, or alternatively, consisting essentiallyof specific steps, but utilize a catalyst system comprising recitedcomponents and other non-recited components.

While compositions and methods are described in terms of “comprising”(or other broad term) various components and/or steps, the compositionsand methods can also be described using narrower terms, such as “consistessentially of” or “consist of” the various components and/or steps.

The terms “a,” “an,” and “the” are intended, unless specificallyindicated otherwise, to include plural alternatives, e.g., at least one.

For any particular compound disclosed herein, the general structure orname presented is also intended to encompass all structural isomers,conformational isomers, and stereoisomers that can arise from aparticular set of substituents, unless indicated otherwise. Thus, ageneral reference to a compound includes all structural isomers, unlessexplicitly indicated otherwise; e.g., a general reference to pentaneincludes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane, while ageneral reference to a butyl group includes an n-butyl group, asec-butyl group, an iso-butyl group, and a tert-butyl group.Additionally, the reference to a general structure or name encompassesall enantiomers, diastereomers, and other optical isomers, whether inenantiomeric or racemic forms, as well as mixtures of stereoisomers, asthe context permits or requires. For any particular formula or name thatis presented, any general formula or name presented also encompasses allconformational isomers, regioisomers, and stereoisomers that can arisefrom a particular set of substituents.

A chemical “group” is described according to how that group is formallyderived from a reference or “parent” compound, for example, by thenumber of hydrogen atoms formally removed from the parent compound togenerate the group, even if that group is not literally synthesized inthis manner. By way of example, an “alkyl group” can formally be derivedby removing one hydrogen atom from an alkane, while an “alkylene group”can formally be derived by removing two hydrogen atoms from an alkane.Moreover, a more general term can be used to encompass a variety ofgroups that formally are derived by removing any number (“one or more”)of hydrogen atoms from a parent compound, which in this example can bedescribed as an “alkane group,” and which encompasses an “alkyl group,”an “alkylene group,” and materials having three or more hydrogens atoms,as necessary for the situation, removed from the alkane. Throughout, thedisclosure of a substituent, ligand, or other chemical moiety that canconstitute a particular “group” implies that the well-known rules ofchemical structure and bonding are followed when that group is employedas described. When describing a group as being “derived by,” “derivedfrom,” “formed by,” or “formed from,” such terms are used in a formalsense and are not intended to reflect any specific synthetic methods orprocedures, unless specified otherwise or the context requiresotherwise.

The term “hydrocarbon” whenever used in this specification and claimsrefers to a compound containing only carbon and hydrogen. Otheridentifiers can be utilized to indicate the presence of particulargroups in the hydrocarbon (e.g., halogenated hydrocarbon indicates thepresence of one or more halogen atoms replacing an equivalent number ofhydrogen atoms in the hydrocarbon). The term “hydrocarbyl group” is usedherein in accordance with the definition specified by IUPAC: a univalentgroup formed by removing a hydrogen atom from a hydrocarbon.Non-limiting examples of hydrocarbyl groups include ethyl, phenyl,tolyl, propenyl, and the like. Similarly, a “hydrocarbylene group”refers to a group formed by removing two hydrogen atoms from ahydrocarbon, either two hydrogen atoms from one carbon atom or onehydrogen atom from each of two different carbon atoms. Therefore, inaccordance with the terminology used herein, a “hydrocarbon group”refers to a generalized group formed by removing one or more hydrogenatoms (as necessary for the particular group) from a hydrocarbon. A“hydrocarbyl group,” “hydrocarbylene group,” and “hydrocarbon group” canbe acyclic or cyclic groups, and/or can be linear or branched. A“hydrocarbyl group,” “hydrocarbylene group,” and “hydrocarbon group” caninclude rings, ring systems, aromatic rings, and aromatic ring systems,which contain only carbon and hydrogen. “Hydrocarbyl groups,”“hydrocarbylene groups,” and “hydrocarbon groups” include, by way ofexample, aryl, arylene, arene, alkyl, alkylene, alkane, cycloalkyl,cycloalkylene, cycloalkane, aralkyl, aralkylene, and aralkane groups,among other groups, as members.

The term “alkane” whenever used in this specification and claims refersto a saturated hydrocarbon compound. Other identifiers can be utilizedto indicate the presence of particular groups in the alkane (e.g.,halogenated alkane indicates the presence of one or more halogen atomsreplacing an equivalent number of hydrogen atoms in the alkane). Theterm “alkyl group” is used herein in accordance with the definitionspecified by IUPAC: a univalent group formed by removing a hydrogen atomfrom an alkane. Similarly, an “alkylene group” refers to a group formedby removing two hydrogen atoms from an alkane (either two hydrogen atomsfrom one carbon atom or one hydrogen atom from two different carbonatoms). An “alkane group” is a general term that refers to a groupformed by removing one or more hydrogen atoms (as necessary for theparticular group) from an alkane. An “alkyl group,” “alkylene group,”and “alkane group” can be acyclic or cyclic groups, and/or can be linearor branched unless otherwise specified. Primary, secondary, and tertiaryalkyl group are derived by removal of a hydrogen atom from a primary,secondary, and tertiary carbon atom, respectively, of an alkane. Then-alkyl group can be derived by removal of a hydrogen atom from aterminal carbon atom of a linear alkane.

An aliphatic compound is an acyclic or cyclic, saturated or unsaturatedcarbon compound, excluding aromatic compounds. Thus, an aliphaticcompound is an acyclic or cyclic, saturated or unsaturated carboncompound, excluding aromatic compounds; that is, an aliphatic compoundis a non-aromatic organic compound. An “aliphatic group” is ageneralized group formed by removing one or more hydrogen atoms (asnecessary for the particular group) from a carbon atom of an aliphaticcompound. Thus, an aliphatic compound is an acyclic or cyclic, saturatedor unsaturated carbon compound, excluding aromatic compounds. That is,an aliphatic compound is a non-aromatic organic compound. Aliphaticcompounds and therefore aliphatic groups can contain organic functionalgroup(s) and/or atom(s) other than carbon and hydrogen.

The term “substituted” when used to describe a compound or group, forexample, when referring to a substituted analog of a particular compoundor group, is intended to describe any non-hydrogen moiety that formallyreplaces a hydrogen in that group, and is intended to be non-limiting. Agroup or groups can also be referred to herein as “unsubstituted” or byequivalent terms, such as “non-substituted,” which refers to theoriginal group in which a non-hydrogen moiety does not replace ahydrogen within that group. “Substituted” is intended to be non-limitingand include inorganic substituents or organic substituents.

The term “olefin” whenever used in this specification and claims refersto hydrocarbons that have at least one carbon-carbon double bond that isnot part of an aromatic ring or an aromatic ring system. The term“olefin” includes aliphatic and aromatic, cyclic and acyclic, and/orlinear and branched hydrocarbons having at least one carbon-carbondouble bond that is not part of an aromatic ring or ring system unlessspecifically stated otherwise. Olefins having only one, only two, onlythree, etc., carbon-carbon double bonds can be identified by use of theterm “mono,” “di,” “tri,” etc., within the name of the olefin. Theolefins can be further identified by the position of the carbon-carbondouble bond(s).

The term “alkene” whenever used in this specification and claims refersto a linear or branched aliphatic hydrocarbon olefin that has one ormore carbon-carbon double bonds. Alkenes having only one, only two, onlythree, etc., such multiple bonds can be identified by use of the term“mono,” “di,” “tri,” etc., within the name. For example, alkamonoenes,alkadienes, and alkatrienes refer to linear or branched acyclichydrocarbon olefins having only one carbon-carbon double bond (acyclichaving a general formula of C_(n)H_(2n)), only two carbon-carbon doublebonds (acyclic having a general formula of C_(n)H_(2n-2)), and onlythree carbon-carbon double bonds (acyclic having a general formula ofC_(n)H_(2n-4)), respectively. Alkenes can be further identified by theposition of the carbon-carbon double bond(s). Other identifiers can beutilized to indicate the presence or absence of particular groups withinan alkene. For example, a haloalkene refers to an alkene having one ormore hydrogen atoms replaced with a halogen atom.

The term “alpha olefin” as used in this specification and claims refersto an olefin that has a carbon-carbon double bond between the first andsecond carbon atoms of the longest contiguous chain of carbon atoms. Theterm “alpha olefin” includes linear and branched alpha olefins unlessexpressly stated otherwise. In the case of branched alpha olefins, abranch can be at the 2 position (a vinylidene) and/or the 3 position orhigher with respect to the olefin double bond. The term “vinylidene”whenever used in this specification and claims refers to an alpha olefinhaving a branch at the 2 position with respect to the olefin doublebond. By itself, the term “alpha olefin” does not indicate the presenceor absence of other carbon-carbon double bonds unless explicitlyindicated.

The term “normal alpha olefin” whenever used in this specification andclaims refers to a linear aliphatic mono-olefin having a carbon-carbondouble bond between the first and second carbon atoms. It is noted that“normal alpha olefin” is not synonymous with “linear alpha olefin” asthe term “linear alpha olefin” can include linear olefinic compoundshaving a double bond between the first and second carbon atoms.

The terms “lights,” “light fraction,” or “light compounds” whenever usedin this specification and claims refers to compounds present in thereaction product with equal to or less than about 9 carbon atoms (C⁹⁻)per molecule. Nonlimiting examples of C⁹⁻ compounds that can be in thereaction product include C⁹⁻ monoolefins (e.g., unreacted C⁹⁻monoolefins), C⁹⁻ mercaptans, C⁹⁻ alkanes, C⁹⁻ alcohols, cyclohexane,methylcyclopentane, methylcyclohexane, benzene, toluene, ethylbenzene,xylene, mesitylene, 2-ethyl-1-hexanol, and the like, or combinationsthereof. Unless otherwise specifically indicated herein, the terms“lights,” “light fraction,” or “light compounds” whenever used in thisspecification and claims excludes hydrogen sulfide, as H₂S is typicallysubstantially consumed during the preceding reaction and/or removed fromthe reaction product (as discussed in more detail herein) prior tofurther processing of the reaction product (e.g., distillation thereof).For example, H₂S can be removed from the reaction product viadistillation, stripping, flashing, or other suitable means known tothose of skill in the art without removing any substantial amounts ofthe “lights,” “light fraction,” or “light compounds” from the reactionproduct. Not wanting to be limited by theory, this definition of“lights,” “light fraction,” or “light compounds” includes any compoundswith about nine or less carbon atoms present in the reaction productthat can be detected, even in trace amounts. As is known to one of skillin the art, the light fraction can also contain trace amounts of lowercarbon number sulfides.

The terms “intermediates” or “intermediate fraction” whenever used inthis specification and claims typically refers to compounds with aboutten to seventeen carbon atoms (C₁₀₋₁₇) per molecule. Nonlimitingexamples of C₁₀₋₁₇ compounds include C₁₀ mercaptans (including bothbranched and non-branched C₁₀ mercaptans), C₁₂₋₁₇ mercaptan isomers,C₁₂-C₁₇ sulfides, and the like, or combinations thereof. Not wanting tobe limited by theory, this definition of “intermediates” or“intermediate fraction” includes any compounds with about ten toseventeen carbon atoms present in the reaction product that can bedetected, even in trace amounts. As is known to one skilled in the art,the intermediate fraction can also contain trace amounts of lower carbonnumber compounds, including sulfides. In some embodiments, a product canbe recovered from the intermediate fraction (e.g., a C₁₀ mercaptanfraction), and the remaining C₁₁ to C₁₇ compounds (e.g., C₁₂₋₁₆mercaptans) can be referred to as the intermediate fraction.

The terms “heavies” or “heavy fraction” whenever used in thisspecification and claims refers to compounds with about eighteen or morecarbon atoms (C₁₈₊) per molecule. Nonlimiting examples of C₁₈₊ productsinclude C₁₈ sulfides, C₂₀ sulfides, C₂₄ sulfides, C₂₈ sulfides, C₃₂sulfides, C₁₈ mercaptans, and the like, or combinations thereof. As isknown to those of skill in the art, the heavy fraction can also containtrace amounts of lower carbon number compounds, including mercaptans andsulfides.

These light, intermediate, and heavy fractions can be referred to as“rough-cuts,” in that they contain a plurality of compounds spreadacross a range of carbon atoms, i.e., a plurality of compounds having adifferent number of carbon atoms (e.g., a rough cut comprising C₁₀, C₁₁,C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, etc. compounds). These rough cuts are incontrast to one or more “fine-cuts” that contain a fewer number ofcompounds than the rough-cuts, for example, a C₁₀ fine cut (e.g., a C₁₀mercaptan fraction) derived from or otherwise recovered separately fromthe rough cut. Accordingly, a rough cut can be comprised of a number offine cuts, for example where a plurality of cuts are taken viadistillation over a period of time and across a ramped temperaturerange, and referred to collectively as a rough cut or individually asfine cuts. Those of ordinary skill in the art can produce a fine-cutfraction from a rough-cut fraction, for example via further distillation(e.g., a C₁₀ splitter, a C₂₀ splitter, etc.) or other purificationtechnique.

The terms “room temperature” or “ambient temperature” are used herein todescribe any temperature from 15° C. to 35° C. wherein no external heator cooling source is directly applied to the reaction vessel.Accordingly, the terms “room temperature” and “ambient temperature”encompass the individual temperatures and any and all ranges, subranges,and combinations of subranges of temperatures from 15° C. to 35° C.wherein no external heating or cooling source is directly applied to thereaction vessel. The term “atmospheric pressure” is used herein todescribe an earth air pressure wherein no external pressure modifyingmeans is utilized. Generally, unless practiced at extreme earthaltitudes, “atmospheric pressure” is about 1 atmosphere (alternatively,about 14.7 psi or about 101 kPa).

Features within this disclosure that are provided as a minimum value canbe alternatively stated as “at least” or “greater than or equal to” anyrecited minimum value for the feature disclosed herein. Features withinthis disclosure that are provided as a maximum value can bealternatively stated as “less than or equal to” or “below” any recitedmaximum value for the feature disclosed herein.

Within this disclosure, the normal rules of organic nomenclature willprevail. For instance, when referencing substituted compounds or groups,references to substitution patterns are taken to indicate that theindicated group(s) is (are) located at the indicated position and thatall other non-indicated positions are hydrogen. For example, referenceto a 4-substituted phenyl group indicates that there is a non-hydrogensubstituent located at the 4 position and hydrogens located at the 2, 3,5, and 6 positions. By way of another example, reference to a3-substituted naphth-2-yl indicates that there is a non-hydrogensubstituent located at the 3 position and hydrogens located at the 1, 4,5, 6, 7, and 8 positions. References to compounds or groups havingsubstitutions at positions in addition to the indicated position will bereferenced using comprising or some other alternative language. Forexample, a reference to a phenyl group comprising a substituent at the 4position refers to a phenyl group having a non-hydrogen substituentgroup at the 4 position and hydrogen or any non-hydrogen group at the 2,3, 5, and 6 positions.

Use of the term “optionally” with respect to any element of a claim isintended to mean that the subject element is required, or alternatively,is not required. Both alternatives are intended to be within the scopeof the claim.

Unless otherwise specified, any carbon-containing group for which thenumber of carbon atoms is not specified can have, according to properchemical practice, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15,16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 carbonatoms, or any range or combination of ranges between these values. Forexample, unless otherwise specified, any carbon-containing group canhave from 1 to 30 carbon atoms, from 1 to 25 carbon atoms, from 1 to 20carbon atoms, from 1 to 15 carbon atoms, from 1 to 10 carbon atoms, orfrom 1 to 5 carbon atoms. Moreover, other identifiers or qualifyingterms can be utilized to indicate the presence or absence of aparticular substituent, a particular regiochemistry and/orstereochemistry, or the presence or absence of a branched underlyingstructure or backbone.

Processes and/or methods described herein utilize steps, features, andcompounds which are independently described herein. The process andmethods described herein may or may not utilize step identifiers (e.g.,1), 2), etc., a), b), etc., or i), ii), etc.), features (e.g., 1), 2),etc., a), b), etc., or i), ii), etc.), and/or compound identifiers(e.g., first, second, etc.). However, it should be noted that processesand/or methods described herein can have multiple steps, features (e.g.,reagent ratios, formation conditions, among other considerations),and/or multiple compounds having the same general descriptor.Consequently, it should be noted that the processes and/or methodsdescribed herein can be modified to use an appropriate step or featureidentifier (e.g., 1), 2), etc., a), b), etc., or i), ii), etc.) and/orcompound identifier (e.g., first, second, etc.) regardless of step,feature, and/or compound identifier utilized in a particular aspectand/or embodiment described herein and that step or feature identifierscan be added and/or modified to indicate individual differentsteps/features/compounds utilized within the process and/or methodswithout detracting from the general disclosure.

Embodiments disclosed herein can provide the materials listed assuitable for satisfying a particular feature of the embodiment delimitedby the term “or.” For example, a particular feature of the disclosedsubject matter can be disclosed as follows: Feature X can be A, B, or C.It is also contemplated that for each feature the statement can also bephrased as a listing of alternatives such that the statement “Feature Xis A, alternatively B, or alternatively C” is also an embodiment of thepresent disclosure whether or not the statement is explicitly recited.

The weight percent compositional aspects of the various compositionsdescribed herein (e.g., the weight percent of one or more compoundspresent in a composition) can be determined by gas chromatography (GC),gas chromatography-mass spectroscopy (GC-MS), Raman spectroscopy,nuclear magnetic resonance (NMR) spectroscopy, or any other suitableanalytical method known to those of skill in the art. For example,unless otherwise indicated, the weight percent compositional aspects ofthe various compositions described herein (e.g., the weight percent ofthe various sulfur-containing compounds such as C₁₀ mercaptans and C₂₀sulfides present in the compositions such as the crude, light fraction,intermediate fraction, heavy faction, etc.) can be determined using agas chromatograph with a flame ionization detector (GC-FID) detectorbased on the total GC peak areas (as described herein) and reported asgas chromatography (GC) area percent (GC area %), which is a commonanalytical technique for compositions comprising sulfur-containingcompounds. While not wishing to be bound by this theory, it is believedthat the amount in area % is very similar to the amount in weightpercent (wt. %), and these respective amounts need not be exactlyequivalent or interchangeable in order to be understood by a person ofordinary skill.

In an embodiment, a process of the present disclosure comprisesreacting, in a reactor, hydrogen sulfide (H₂S) and a feedstockcomprising one or more branched C₁₀ monoolefins in the presence of aninitiating agent to produce a crude composition (also referred to as acrude product); wherein the branched C₁₀ monoolefins comprise5-methyl-1-nonene, 3-propyl-1-heptene, 4-ethyl-1-octene,2-butyl-1-hexene, or combinations thereof; and wherein the crudecomposition comprises branched C₁₀ mercaptans and branched C₂₀ sulfides.

The crude composition can be further processed, for example viadistillation, to yield one or more products (also referred to asdistilled, purified, refined, finished, or final products) selected fromthe group consisting of mercaptan compositions (e.g., a compositioncomprising one or more branched C₁₀ mercaptans), sulfide compositions(e.g., a composition comprising one or more branched C₂₀ sulfides); andcompositions having both mercaptans (e.g., branched C₁₀ mercaptans) andsulfides (e.g., branched C₂₀ sulfides), referred to as mercaptan/sulfidecompositions.

In an embodiment, a mercaptan composition comprises branched C₁₀mercaptans selected from the group consisting of5-methyl-1-mercapto-nonane, 3-propyl-1-mercapto-heptane,4-ethyl-1-mercapto-octane, 2-butyl-1-mercapto-hexane,5-methyl-2-mercapto-nonane, 3-propyl-2-mercapto-heptane,4-ethyl-2-mercapto-octane, 5-methyl-5-mercapto-nonane, and combinationsthereof.

In an embodiment, a sulfide composition comprises branched C₂₀ sulfidesrepresented by the structure R¹—S—R², wherein R¹ and R² are eachindependently a functional group derived from an olefin, wherein theolefin comprises 5-methyl-1-nonene, 3-propyl-1-heptene,4-ethyl-1-octene, 2-butyl-1-hexene, or combinations thereof.

In an embodiment, a mercaptan/sulfide composition comprises (A) branchedC₁₀ mercaptans selected from the group consisting of5-methyl-1-mercapto-nonane, 3-propyl-1-mercapto-heptane,4-ethyl-1-mercapto-octane, 2-butyl-1-mercapto-hexane,5-methyl-2-mercapto-nonane, 3-propyl-2-mercapto-heptane,4-ethyl-2-mercapto-octane, 5-methyl-5-mercapto-nonane, and combinationsthereof; and (B) branched C₂₀ sulfides represented by the structureR¹—S—R², wherein R¹ and R² are each independently a functional groupderived from an olefin, wherein the olefin comprises 5-methyl-1-nonene,3-propyl-1-heptene, 4-ethyl-1-octene, 2-butyl-1-hexene, or combinationsthereof.

The mercaptan compositions, sulfide compositions, and mercaptan/sulfidecompositions can be salable or otherwise used for a variety of end usessuch as mining ore collector compositions and chain transfer agents.

In an embodiment, the compositions disclosed herein can be prepared by aprocess comprising reacting, in a reactor, hydrogen sulfide (H₂S) and afeedstock comprising one or more branched C₁₀ monoolefins in thepresence of an initiating agent to produce a crude (reaction product)composition, wherein the branched C₁₀ monoolefins comprise5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

Any feedstock comprising one or more branched C₁₀ monoolefins of thetype described herein can be used, for example a feedstock obtained froma commercial petroleum refining or petrochemical process. Suchfeedstocks can comprise other olefins in addition to the one or morebranched C₁₀ monoolefins of the type described herein, for examplelinear C₁₀ monoolefins as well as olefins having more or less than 10carbon atoms. In an embodiment, the feedstock comprises one or morebranched C₁₀ monoolefins and is obtained from a 1-hexene productionprocess effluent stream. In various embodiments, a feedstock obtainedfrom a 1-hexene production process effluent stream can comprise C₁₀monoolefins (e.g., branched and/or linear C₁₀ monoolefins) as well asolefins having more or less than 10 carbon atoms.

In an embodiment, the feedstock can comprise (a) at least about 76 mol%, alternatively at least about 78 mol %, alternatively at least about80 mol %, or alternatively at least about 82 mol % C₁₀ monoolefins, and(b) at least about 1 mol %, alternatively at least about 2 mol %,alternatively at least about 3 mol %, or alternatively at least about 4mol % C₁₄ monoolefins. In an embodiment, the feedstock can comprise (a)from about 76 mol % to about 92 mol %, alternatively from about 78 mol %to about 90 mol %, alternatively from about 80 mol % to about 88 mol %,or alternatively from about 82 mol % to about 86 mol % C₁₀ monoolefins;and (b) from about 1 mol % to about 12 mol %, alternatively from about 2mol % to about 10 mol %, alternatively from about 3 mol % to about 8 mol%, or alternatively from about 4 mol % to about 7 mol % C₁₄ monoolefins.For purposes of the disclosure herein, a feedstock comprising (a) atleast about 76 mol % C₁₀ monoolefins, and (b) at least about 1 mol % C₁₄monoolefins can also be referred to as a “first feedstock.” In anembodiment, the first feedstock is obtained from a 1-hexene productionprocess effluent stream, for example an effluent stream obtained from a1-hexene production process of the type disclosed in co-pendingInternational Patent Application PCT/US2015/40433, which is incorporatedby reference herein in its entirety.

In another embodiment, the feedstock can comprise at least about 95 mol%, alternatively at least about 96 mol %, alternatively at least about97 mol %, alternatively at least about 98 mol %, or alternatively atleast about 99 mol % C₁₀ monoolefins. For purposes of the disclosureherein, a feedstock comprising at least about 95 mol % C₁₀ monoolefinscan also be referred to as a “second feedstock.” In an embodiment, thesecond feedstock can be produced by purifying the first feedstock, suchas for example by distillation of an effluent stream obtained from a1-hexene production process of the type disclosed in co-pendingInternational Patent Application PCT/US2015/40433, which is incorporatedby reference herein in its entirety.

In an embodiment, the C₁₀ monoolefins of any feedstock described herein(e.g., a first feedstock or a second feedstock) can comprise, canconsist essentially of, or can be, 2-butyl-1-hexene, 3-propyl-1-heptene,4-ethyl-1-octene, and 5-methyl-1-nonene. In an embodiment, the C₁₀monoolefins of any feedstock described herein can comprise i) at leastabout 3 mol %, alternatively at least about 4 mol %, alternatively atleast about 5 mol %, alternatively at least about 6 mol %, alternativelyat least about 7 mol %, or alternatively at least about 8 mol %2-butyl-1-hexene (represented by Structure L), ii) at least about 8 mol%, alternatively at least about 9 mol %, alternatively at least about 10mol %, alternatively at least about 11 mol %, alternatively at leastabout 12 mol %, or alternatively at least about 13 mol %3-propyl-1-heptene (represented by Structure J), iii) at least about 6mol %, alternatively at least about 7 mol %, alternatively at leastabout 8 mol %, alternatively at least about 9 mol %, alternatively atleast about 10 mol %, or alternatively at least about 11 mol %4-ethyl-1-octene (represented by Structure K), and iv) at least about 20mol %, alternatively at least about 22 mol %, alternatively at leastabout 24 mol %, alternatively at least about 26 mol %, alternatively atleast about 28 mol %, or alternatively at least about 30 mol %5-methyl-1-nonene (represented by Structure I).

In an embodiment, the C₁₀ monoolefins of any feedstock described herein(e.g., a first feedstock or a second feedstock) can have a molar ratioof 2-butyl-1-hexene to 5-methyl-1-nonene of at least about 2:1,alternatively at least about 2.4:1, alternatively at least about 2.6:1,or alternatively at least about 2.8:1. In an embodiment, the C₁₀monoolefins of any feedstock described herein can have a molar ratio of3-propyl-1-heptene to 5-methyl-1-nonene of at least about 1.2:1,alternatively at least about 1.4:1, alternatively at least about 1.6:1,or alternatively at least about 1.8:1. In an embodiment, the C₁₀monoolefins of any feedstock described herein can have a molar ratio of4-ethyl-1-octene to 5-methyl-1-nonene of at least about 1.6:1,alternatively at least about 1.7:1, alternatively at least about 1.9:1,or alternatively at least about 2.1:1. In an embodiment, the C₁₀monoolefins of any feedstock described herein can have a molar ratio of2-butyl-1-hexene to 5-methyl-1-nonene of at least about 2:1,alternatively at least about 2.4:1, alternatively at least about 2.6:1,or alternatively at least about 2.8:1; a molar ratio of3-propyl-1-heptene to 5-methyl-1-nonene of at least about 1.2:1,alternatively at least about 1.4:1, alternatively at least about 1.6:1,or alternatively at least about 1.8:1; and a molar ratio of4-ethyl-1-octene to 5-methyl-1-nonene of at least about 1.6:1,alternatively at least about 1.7:1, alternatively at least about 1.9:1,or alternatively at least about 2.1:1.

In an embodiment, the C₁₀ monoolefins of any feedstock described herein(e.g., a first feedstock or a second feedstock) can comprise linear C₁₀monoolefins. In such embodiment, the linear C₁₀ monoolefins cancomprise, can consist essentially of, or can be, 1-decene, 4-decene,5-decene, or combinations thereof; alternatively, 1-decene;alternatively, 4-decene and/or 5-decene; alternatively, 4-decene; oralternatively, 5-decene. In an embodiment, the C₁₀ monoolefins of anyfeedstock described herein can comprise less than or equal to about 26mol %, alternatively less than or equal to about 24 mol %, alternativelyless than or equal to about 22 mol %, alternatively less than or equalto about 20 mol %, or alternatively less than or equal to about 18 mol %linear C₁₀ monoolefins. In an embodiment, the C₁₀ monoolefins of anyfeedstock described herein can comprise from about 1 mol % to about 16mol %, alternatively from about 2 mol % to about 15 mol %, alternativelyfrom about 3 mol % to about 14 mol %, alternatively from about 4 mol %to about 13 mol %, or alternatively from about 6 mol % to about 12 mol %4-decene and/or 5-decene. In some embodiments, the C₁₀ monoolefins ofany feedstock described herein can comprise less than or equal to about10 mol %, alternatively less than or equal to about 9 mol %,alternatively less than or equal to about 8 mol %, alternatively lessthan or equal to about 7 mol %, or alternatively less than or equal toabout 6 mol % 1-decene. In other embodiments, the C₁₀ monoolefins of anyfeedstock described herein can comprise from about 0.5 mol % to about 9mol %, alternatively from about 1 mol % to about 8 mol %, alternativelyfrom about 1.5 mol % to about 7 mol %, or alternatively from about 2 mol% to about 6 mol %1-decene.

In an embodiment, the first feedstock disclosed herein can furthercomprise C⁹⁻ monoolefins, C₁₁₊ monoolefins, or combinations thereof;alternatively, C⁹⁻ monoolefins; or alternatively, C₁₁₊ monoolefins. Inan embodiment, the C⁹⁻ monoolefins can comprise, can consist essentiallyof, or can be, a C₇ monoolefin, a C₈ monoolefin, a C₉ monoolefin, orcombinations thereof; alternatively, a C₇ monoolefin; alternatively, aC₈ monoolefin; or alternatively, a C₉ monoolefin. In some embodiments,the C⁹⁻ monoolefins can comprise, can consist essentially of, or can be,a C₈ monoolefin. In an embodiment, the C₁₁₊ monoolefins can comprise,can consist essentially of, or can be, a C₁₁ monoolefin, a C₁₂monoolefin, a C₁₃ monoolefin, a C₁₄ monoolefin, a C₁₅ monoolefin, a C₁₆monoolefin, a C₁₇ monoolefin, a C₁₈ monoolefin, or combinations thereof;alternatively, a C₁₁ monoolefin; alternatively, a C₁₂ monoolefin;alternatively, a C₁₃ monoolefin; alternatively, a C₁₄ monoolefin;alternatively, a C₁₅ monoolefin; alternatively, a C₁₆ monoolefin;alternatively, a C₁₇ monoolefin; or alternatively, a C₁₈ monoolefin. Insome embodiments, the C₁₁₊ monoolefins can comprise, can consistessentially of, or can be, a C₁₂ monoolefin, a C₁₆ monoolefin, a C₁₈monoolefin, or combinations thereof; alternatively, a C₁₂ monoolefin;alternatively, a C₁₆ monoolefin; or alternatively, a C₁₈ monoolefin.

In an embodiment, the first feedstock disclosed herein can furthercomprise C₈ monoolefins, C₁₂ monoolefins, C₁₆ monoolefins, C₁₈monoolefins, or combinations thereof; alternatively, C₈ monoolefins;alternatively, C₁₂ monoolefins; alternatively, C₁₆ monoolefins and/orC₁₈ monoolefins; alternatively, C₁₆ monoolefins; or alternatively, C₁₈monoolefins. In an embodiment, the C₈ monoolefins can comprise 1-octene.In an embodiment, the C₁₂ monoolefins can comprise 1-dodecene.

In an embodiment, the first feedstock can further comprise from about0.1 mol % to about 5 mol %, alternatively from about 0.25 mol % to about4 mol %, or alternatively from about 0.5 mol % to about 3 mol % C₁₂monoolefins. In such embodiment, the C₁₂ monoolefins can comprise fromabout 54 mol % to about 74 mol %, alternatively from about 56 mol % toabout 72 mol %, alternatively from about 58 mol % to about 70 mol %, oralternatively from about 60 mol % to about 68 mol % 1-dodecene.

In an embodiment, the first feedstock can further comprise from about0.1 mol % to about 5 mol %, alternatively from about 0.25 mol % to about4 mol %, or alternatively from about 0.5 mol % to about 3 mol % C₈monoolefins. In such embodiment, the C₈ monoolefins can comprise atleast about 95 mol %, alternatively at least about 96 mol %,alternatively at least about 97 mol %, alternatively at least about 98mol %, or alternatively at least about 99 mol % 1-octene.

In an embodiment, the first feedstock can further comprise from about0.05 mol % to about 2 mol %, alternatively from about 0.04 mol % toabout 1.5 mol %, alternatively from about 0.06 mol % to about 1.25 mol%, alternatively from about 0.08 mol % to about 1 mol %, oralternatively from about 0.1 mol % to about 0.75 mol % C₁₆ monoolefinsand/or C₁₈ monoolefins.

In an embodiment, a feedstock comprising branched C₁₀ monoolefinsproduced in a 1-hexene process can be purified to produce a secondfeedstock of the type described herein, for example to improve olefinreactivity and resultant mercaptan and/or sulfide purity. A lightfraction, comprising C⁹⁻, can be removed from the feedstock and any C₁₀olefin isomers can be collected overhead to obtain a high purity (>95%)C₁₀ monoolefin fraction as the second feedstock. This high purity C₁₀monoolefin fraction (i.e., second feedstock) comprises little or nonon-olefin impurities or C₁₁ to C₁₇ compounds. The high purity C₁₀olefin can be reacted with H₂S to produce a crude composition. Reactionconditions to produce a crude composition from the high purity C₁₀monoolefin fraction (i.e., a second feedstock) can be identical to thereaction conditions disclosed for the feedstock comprising branched C₁₀monoolefins produced in a 1-hexene process used as received withoutfurther purification (i.e., a first feedstock). The major differencebetween reacting a first feedstock and a second feedstock is thecomposition of the crude composition and any resulting purified orpartially purified products (e.g., fractions or cuts taken from thecrude composition). For the second feedstock (e.g., a high purity (>95%)C₁₀ monoolefin fraction), the crude composition can comprise residualH₂S, unreacted C₁₀ olefin, C₁₀ mercaptan isomers, and C₁₀H₂₁—S—C₁₀H₂₁sulfides and minimal other mercaptans or sulfides. After removal of H₂Sand C⁹⁻ lights from the crude composition, the resultant partiallypurified product will contain C₁₀ mercaptan isomers and C₂₀ sulfides,but will not contain any of the intermediate mercaptans and asymmetricsulfide components formed by reactions of olefins having less than orgreater than 10 carbon atoms (because there were minimal, if any, sucholefins having less than or greater than 10 carbon atoms in the purifiedfeedstock). While not wishing to be bound by theory, it is believed thatthe intermediate mercaptans and asymmetric sulfide components can beproduced from the reaction of C₁₀ mercaptans with other non-C₁₀ olefins.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted at an H₂S to olefin molar ratio of fromabout 1:1 to about 20:1, alternatively from about 2:1 to about 15:1, oralternatively from about 3:1 to about 10:1.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted at a pressure of from about 30 psig (206kPag) to about 1,500 (10,300 kPag) psig, alternatively from about 100psig (690 kPag) to about 1,250 psig (8,600 kPag), or alternatively fromabout 250 (1,700 kPag) psig to about 1,000 psig (6,900 kPag).

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted to produce olefin conversion of equal toor greater than about 80%, alternatively equal to or greater than about85%, or alternatively equal to or greater than about 90%. For purposesof the disclosure herein, an olefin conversion refers to the mol % ofolefins that have reacted during the reaction between H₂S and afeedstock in a reactor, with respect to the amount of olefins introducedinto the reactor during the same time period.

In an embodiment, the process can comprise reacting H₂S and a feedstock(e.g., a first or second feedstock as described herein) comprising oneor more branched C₁₀ monoolefins in the presence of an initiating agentto produce a crude composition; wherein the initiating agent comprisesultraviolet (UV) radiation. In such embodiment, the UV radiation can beany UV radiation capable of initiating the reaction of the olefinspresent in the feedstock and H₂S. In some embodiments, the UV radiationcan be generated by a medium pressure mercury lamp. As will beappreciated by one of skill in the art, and with the help of thisdisclosure, although UV radiation can be the initiating agent, othersuitable types of light sources can be used.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted in the presence of an initiating agentcomprising UV radiation in a batch reactor or a continuous reactor.Nonlimiting examples of continuous reactors suitable for use in thepresent disclosure include continuous flow reactors, continuous stirredreactors, fixed bed reactors, and the like, or combinations thereof.Nonlimiting examples of batch reactors suitable for use in the presentdisclosure include UV batch reactors. As will be appreciated by one ofskill in the art, and with the help of this disclosure, any othersuitable type of batch and continuous reactors can be used for reactingH₂S and a feedstock comprising one or more branched C₁₀ monoolefins inthe presence of UV radiation. UV reactors and conditions suitable forreacting H₂S and a feedstock comprising one or more branched C₁₀monoolefins in the presence of UV radiation are described in more detailin U.S. Pat. No. 7,989,655, and U.S. Publication No. 20140221692 A1,each of which is incorporated by reference herein in its entirety.

In embodiments where H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins are reacted in the presence of UV radiation in acontinuous reactor, the continuous reactor can be sized and configuredto the desired continuous production rate. That is, a person skilled inthe art will be able to select an appropriate reaction vessel size,geometry and material (e.g., a transparent material for sidewalls,windows, or internal chambers); along with an appropriate number of UVsources; and arrange the sources and reactor vessel (e.g., place UVsources adjacent a transparent exterior portion of the reaction vesseland/or disposed in transparent chambers within the reactor vessel) toyield a desired continuous production rate.

In embodiments where H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins are reacted in the presence of UV radiation in a batchreactor, the batch reactor can be characterized by a reaction time offrom about 1 minute to about 4 hours, alternatively from about 10minutes to about 2 hours, or alternatively from about 30 minutes toabout 1.5 hours.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted in the presence of UV radiation at atemperature of from about 0° C. to about 100° C., alternatively fromabout 10° C. to about 70° C., or alternatively from about 15° C. toabout 35° C.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted in the presence of UV radiation at a H₂Sto olefin molar ratio of from about 1:1 to about 15:1, alternativelyfrom about 2:1 to about 12.5:1, or alternatively from about 5:1 to about10:1.

In an embodiment, the process can comprise reacting H₂S and a feedstockcomprising one or more branched C₁₀ monoolefins in the presence of aninitiating agent to produce a crude composition; wherein the initiatingagent comprises ultraviolet (UV) radiation, and wherein the initiatingagent further comprises a phosphite promoter, a photoinitiator, or both.

In an embodiment, the phosphite promoter can be used in an amount offrom about 0.01 wt. % to about 5 wt. %, alternatively from about 0.1 wt.% to about 4 wt. %, or alternatively from about 1 wt. % to about 2.5 wt.%, based on a weight of olefins.

In an embodiment, the phosphite promoter can be characterized by formulaP(OR⁵)₃, wherein each R⁵ can independently be a C₁-C₁₈ hydrocarbylgroup, alternatively C₁-C₁₀ hydrocarbyl group, alternatively C₁-C₅hydrocarbyl group; alternatively a C₁-C₁₈ alkyl group, alternativelyC₁-C₁₀ alkyl group, alternatively C₁-C₅ alkyl group; alternatively, aC₆-C₁₈ aryl group, or alternatively, a C₆-C₁₀ aryl group. Nonlimitingexamples of R⁵ groups suitable for use in the present disclosure in thephosphite promoter include a methyl group, an ethyl group, a propylgroup, a butyl group, a pentyl group, a hexyl group, a heptyl group, anoctyl group, a nonyl group, a decyl group; a phenyl group, a tolylgroup, a xylyl group, a naphthyl group; and the like, or combinationsthereof.

Nonlimiting examples of phosphite promoters suitable for use in thepresent disclosure include a trialkylphosphite, trimethylphosphite,triethylphosphite, tributylphosphite; a triarylphosphite,triphenylphosphite; and the like, or combinations thereof.

In an embodiment, the photoinitiator can be used in an amount of fromabout 0.05 wt. % to about 5 wt. %, alternatively from about 0.1 wt. % toabout 4 wt. %, or alternatively from about 1 wt. % to about 2.5 wt. %,based on the weight of olefins present in the feed mixture.

Nonlimiting examples of photoinitiators suitable for use in the presentdisclosure include 1-hydroxy-cyclohexyl-phenyl-ketone, benzophenone,Bis-(2,4,6-trimethylbenzoyl)-phenylphosphineoxide,2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methy-1-propan-1-one,2-hydroxy-2-methyl-1-phenyl-1-propanone, and the like, or combinationsthereof.

In an embodiment, the process can comprise reacting H₂S and a feedstockcomprising one or more branched C₁₀ monoolefins in the presence of UVradiation to produce a crude composition (wherein the crude compositioncomprises from 50-100 wt. % C₁₀ mercaptans, alternatively from 50-90 wt.% C₁₀ mercaptans, alternatively from 75-85 wt. % C₁₀ mercaptans);wherein the C₁₀ mercaptans present in the crude composition furthercomprise from about 70 wt. % to about 100 wt. %, alternatively fromabout 70 wt. % to about 95 wt. %, alternatively from about 80 wt. % toabout 90 wt. %, or alternatively from about 79 wt. % to about 85 wt. %C₁₀ primary mercaptans; from about 0 wt. % to about 30 wt. %,alternatively from about 0 wt. % to about 20 wt. %, alternatively fromabout 10 wt. % to about 20 wt. %, or alternatively from about 5 wt. % toabout 19 wt. % C₁₀ secondary mercaptans; and from about 0 wt. % to about10 wt. %, alternatively from about 0 wt. % to about 5 wt. %, oralternatively from about 0 wt. % to about 3 wt. % C₁₀ tertiarymercaptans. For purposes of the disclosure herein, a primary mercaptanis a mercaptan that has the thiol group (—SH) attached to a primarycarbon (e.g., a carbon atom that is attached to one and only one othercarbon atom). Further, for purposes of the disclosure herein, asecondary mercaptan is a mercaptan that has the thiol group (—SH)attached to a secondary carbon (e.g., a carbon atom that is attached totwo and only two other carbon atoms). Further, for purposes of thedisclosure herein, a tertiary mercaptan is a mercaptan that has thethiol group (—SH) attached to a tertiary carbon (e.g., a carbon atomthat is attached to three and only three other carbon atoms). As will beappreciated by one of skill in the art, and with the help of thisdisclosure, the make-up of the crude composition, in terms of primary,secondary, and tertiary mercaptans, will depend on the make-up of thefeedstock, as well as on the reaction conditions. Further, as will beappreciated by one of skill in the art, and with the help of thisdisclosure, the make-up of each of the primary, secondary, and tertiarymercaptans will depend on the make-up of the feedstock, as well as onthe reaction conditions.

In an embodiment, the C₁₀ primary mercaptans can comprise5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),1-mercapto-decane (represented by Structure M), or combinations thereof.

In an embodiment, the C₁₀ secondary mercaptans can comprise4-mercapto-decane (represented by Structure N), 5-mercapto-decane(represented by Structure 0), 5-methyl-2-mercapto-nonane (represented byStructure E), 3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),2-mercapto-decane (represented by Structure P), or combinations thereof.

In an embodiment, the C₁₀ tertiary mercaptans can comprise equal to orgreater than about 90 wt. %, alternatively equal to or greater thanabout 95 wt. %, or alternatively equal to or greater than about 99 wt. %5-methyl-5-mercapto-nonane (represented by Structure H).

In an embodiment, the process can comprise reacting H₂S and a feedstock(e.g., a first or second feedstock as described herein) comprising oneor more branched C₁₀ monoolefins in the presence of an initiating agent(e.g., catalyst) to produce a crude composition; wherein the initiatingagent comprises an acid catalyst. Nonlimiting examples of acid catalystssuitable for use in the present disclosure include acid washed clays(such as, but not limited to, Filtrol® 24 or Filtrol® 24X); acid washedbentonite; a tetrafluoroethylene polymer resin modified withperfluorovinyl ether groups terminated with sulfonate groups; amacroreticular, sulfonated, crosslinked copolymer of styrene and divinylbenzene; and the like, or combinations thereof.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted in the presence of an acid catalyst in acontinuous reactor, such as for example continuous flow reactor,continuous stirred reactors, fixed bed reactors, packed bed reactors,and the like, or combinations thereof.

In embodiments where H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins are reacted in the presence of an acid catalyst in acontinuous reactor, the continuous reactor can be characterized by aweight hourly space velocity (WHSV) of from about 0.1 h⁻¹ to about 5h⁻¹, alternatively from about 0.5 h⁻¹ to about 4 h⁻¹, or alternativelyfrom about 1 h⁻¹ to about 3 h⁻¹, based on mass of olefin per mass ofcatalyst per hour.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted in the presence of an acid catalyst at atemperature of from about 100° C. to about 300° C., alternatively fromabout 120° C. to about 220° C., or alternatively from about 180° C. toabout 200° C.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted in the presence of an acid catalyst at aH₂S to olefin molar ratio of from about 1:1 to about 10:1, alternativelyfrom about 2:1 to about 7.5:1, or alternatively from about 2.5:1 toabout 5:1.

In an embodiment, the process can comprise reacting H₂S and a feedstockcomprising one or more branched C₁₀ monoolefins in the presence of anacid catalyst to produce a crude composition (wherein the crudecomposition comprises from 50-100 wt. % C₁₀ mercaptans, alternativelyfrom 50-90 wt. % C₁₀ mercaptans, alternatively from 75-85 wt. % C₁₀mercaptans); wherein the C₁₀ mercaptans comprise from about 0 wt. % toabout 5 wt. % alternatively from about 0.1 wt. % to about 4 wt. %, oralternatively from about 0.5 wt. % to about 2.5 wt. % C₁₀ primarymercaptans; from about 80 wt. % to about 95 wt. %, alternatively fromabout 82.5 wt. % to about 92.5 wt. %, or alternatively from about 85 wt.% to about 90 wt. % C₁₀ secondary mercaptans; and from about 5 wt. % toabout 20 wt. %, alternatively from about 7.5 wt. % to about 17.5 wt. %,or alternatively from about 10 wt. % to about 15 wt. % C₁₀ tertiarymercaptans.

In an embodiment, the process can comprise reacting H₂S and a feedstock(e.g., a first or second feedstock as described herein) comprising oneor more branched C₁₀ monoolefins in the presence of an initiating agentto produce a crude composition; wherein the initiating agent comprises ahydrodesulfurization (HDS) catalyst.

In an embodiment, the HDS catalyst comprises a comprises a metal, atransition metal, Ru, Co, Mo, Ni, W, sulfides thereof, disulfidesthereof, and the like, or combinations thereof.

In an embodiment, the HDS catalyst can be Haldor Topsoe TK-554 orTK-570, and the like, or combinations thereof.

In an embodiment, the HDS catalyst can further comprise a support, suchas for example alumina, silica, and the like, or combinations thereof.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted in the presence of an HDS catalyst in acontinuous reactor, such as for example continuous flow reactor,continuous stirred reactors, fixed bed reactors, packed bed reactors,and the like, or combinations thereof.

In embodiments where H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins are reacted in the presence of an HDS catalyst in acontinuous reactor, the continuous reactor can be characterized by aWHSV of from about 0.1 h⁻¹ to about 5 h⁻¹, alternatively from about 0.5h⁻¹ to about 4 h⁻¹, or alternatively from about 1 h⁻¹ to about 3 h⁻¹,based on mass of olefin per mass of catalyst per hour.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted in the presence of an HDS catalyst at atemperature of from about 100° C. to about 300° C., alternatively fromabout 120° C. to about 220° C., or alternatively from about 180° C. toabout 200° C.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted in the presence of an HDS catalyst at aH₂S to olefin molar ratio of from about 1:1 to about 10:1, alternativelyfrom about 2:1 to about 7.5:1, or alternatively from about 2.5:1 toabout 5:1.

In an embodiment, the process can comprise reacting H₂S and a feedstockcomprising one or more branched C₁₀ monoolefins in the presence of anHDS catalyst to produce a crude composition (wherein the crudecomposition comprises from 50-100 wt. % C₁₀ mercaptans, alternativelyfrom 50-90 wt. % C₁₀ mercaptans, alternatively from 75-85 wt. % C₁₀mercaptans); wherein the C₁₀ mercaptans comprise from about 5 wt. % toabout 30 wt. % alternatively from about 10 wt. % to about 25 wt. %, oralternatively from about 15 wt. % to about 20 wt. % C₁₀ primarymercaptans; from about 60 wt. % to about 75 wt. %, alternatively fromabout 62.5 wt. % to about 72.5 wt. %, or alternatively from about 65 wt.% to about 70 wt. % C₁₀ secondary mercaptans; and from about 5 wt. % toabout 15 wt. %, alternatively from about 7.5 wt. % to about 13.5 wt. %,or alternatively from about 9 wt. % to about 12 wt. % C₁₀ tertiarymercaptans.

As noted previously, any such feedstocks comprising one or more branchedC₁₀ monoolefins can be reacted with hydrogen sulfide (H₂S) in thepresence of an initiating agent to produce a crude composition, and thecrude composition can be further refined (e.g., distilled or otherwiseseparated into one or more fractions such as lights, intermediate, andheavies) to yield the various compositions described herein. Asdescribed in more detail herein, the type and/or amounts of theconstituent components that form the crude composition can varydepending upon the feedstock (e.g., the amount and types of olefinstherein), the reaction conditions, the catalysts employed, etc., and oneskilled in the art can tailor the post reactor processing of the crudecomposition to account for the specific compounds present in a givencrude composition to yield various desired products and compositions ofthe types described herein.

Upon completion of the reaction of a feedstock comprising one or morebranched C₁₀ monoolefins with hydrogen sulfide (H₂S), a reactor effluentcan be recovered from the reactor and H₂S removed therefrom to yield acrude composition. The term “crude composition” or “crude product”refers to an unrefined effluent stream recovered from the reactor afterremoval of H₂S, and in particular to an H₂S-free effluent stream thathas not undergone any additional post-reactor processing such asflashing, distillation, or other separation techniques or processes toremove any components from the effluent stream other than the initialremoval of H₂S.

Hydrogen sulfide (H₂S) is a highly corrosive, poisonous, flammable,explosive gas. As such, it is typically removed before the crudecomposition can be further processed or utilized. Bulk H₂S can beremoved under conditions of reduced pressure, and residual H₂S can beremoved at reduced temperature and pressure without removing anysubstantial quantities of the lights. Alternatively, H₂S can also beremoved by sparging inert gas into the liquid phase. Alternatively,there are other methods for removing H₂S (i.e., absorption, stripping,etc.) that are known to those of skill in the art. In an embodiment,under appropriate conditions, a reactor effluent can be treated toremove essentially all of any excess and/or unreacted hydrogen sulfide(H₂S).

The crude composition comprises branched C₁₀ mercaptans and branched C₂₀sulfides formed by the reaction of H₂S and the one or more branched C₁₀monoolefins, and the structures of these branched C₁₀ mercaptans andbranched C₂₀ sulfides are described in more detail herein. In additionto branched C₁₀ mercaptans and branched C₂₀ sulfides, the crudecomposition can comprise a number of other compounds such as unreactedolefins, inert compounds (e.g., alkanes), non-branched C₁₀ mercaptans,non-branched C₂₀ sulfides, non-C₁₀ mercaptans, non-C₂₀ sulfides, andother impurities. The constituent components contained within the crudecomposition can vary depending upon the composition of the feedstock(e.g., an unpurified first feedstock as compared to a purified secondfeedstock as described herein) as well as reaction conditions, catalyst,etc. In various embodiments, a crude composition can comprise light,intermediate, and heavy fractions as described herein.

In an embodiment, the crude compositions can contain a variety of othernon-C₁₀ mercaptan and non-C₂₀ sulfides components (e.g., impurities)such as C₈ mercaptans; C₁₂ mercaptans; C₁₄ mercaptans; C₁₆ mercaptans;C₁₈ mercaptans; C₁₆₋₃₆ sulfides represented by the structure R³—S—R⁴,wherein R³ and R⁴ are each independently a functional group derived froman olefin selected from the group consisting of C₈ monoolefins, C₁₀monoolefins, C₁₂ monoolefins, C₁₄ monoolefins, C₁₆ monoolefins, and C₁₈monoolefins, wherein R³ and R⁴ are not both branched C₁₀ monoolefins;unreacted C₈₋₁₈ monoolefins; non-olefin impurities selected from thegroup consisting of C₈₋₁₄ alkanes, cyclohexane, methylcyclopentane,methylcyclohexane, benzene, toluene, ethylbenzene, xylene, mesitylene,hexamethylbenzene, C₄₋₁₂ alcohols, 2-ethyl-1-hexanol, and2-ethylhexyl-2-ethylhexanoate; and combinations thereof.

In an embodiment, a crude composition comprising branched C₁₀ mercaptansand branched C₂₀ sulfides can be separated by any process or unitoperation known in the art. For example, a crude composition can beprocessed (e.g., distilled) to remove a fraction of light compounds.Alternatively, a crude composition can be processed to recover both alights fraction and an intermediates fraction (e.g., a rough cut),followed by further processing to obtain one or more fine cuts.Alternatively, a crude composition can be processed to recover a heaviesfraction (e.g., a C₂₀ sulfide fraction). Alternatively, a crudecomposition can be processed to separate out any combination of a lightsfraction, an intermediates fraction (e.g., comprising C₁₀ mercaptans,including branched C₁₀ mercaptans), and a heavies fraction (e.g.,comprising C₂₀ sulfides, including branched C₂₀ sulfides). Furthermore,a light, intermediate or heavy fraction (e.g., a rough cut) can befurther processed or parsed to obtain one or more desired fine cuts(e.g., a C₁₀ mercaptan fraction). Alternatively, a crude composition canbe separated to produce a high-purity C₁₀ mercaptan stream and/or ahigh-purity C₂₀ sulfide stream (e.g., to obtain a desired fine cut orfraction such as a C₁₀ mercaptan fraction). Further, these separatedstreams can be blended in any combination of ratios to produce a mixturewith specific concentrations of one of more components (e.g., desiredblend ratios of branched C₁₀ mercaptans and/or branched C₂₀ sulfides,for example to aid in a particular end use). The unitoperations/processes used for these separations are known to one ofskill and the art and include, but are not limited to, distillation,fractionation, flashing, stripping, and absorption, and others. The unitoperation conditions, such as for example, temperature, pressure, flowrates, and others at which these unit operations produce one or more ofthe desired fractions can easily be determined by one of ordinary skillin the art.

In an embodiment, a lights fraction is removed from the crudecomposition, for example by flashing, distillation, fractionation,stripping, absorption, etc.

In an embodiment, the lights fraction can comprise at least about 90 wt.%, alternatively at least about 90 wt. %, alternatively at least about95 wt. %, alternatively at least about 96 wt. %, alternatively at leastabout 97 wt. %, alternatively at least about 98 wt. %, alternatively atleast about 99 wt. % C⁹⁻ compounds, based on the total weight of thelights fraction. Nonlimiting examples of C⁹⁻ compounds include C⁹⁻monoolefins (e.g., unreacted C⁹⁻ monoolefins), C⁹⁻ mercaptans, C⁹⁻alkanes, cyclohexane, methylcyclopentane, methylcyclohexane, benzene,toluene, ethylbenzene, xylene, mesitylene, C⁹⁻ alcohols,2-ethyl-1-hexanol, and the like, or combinations thereof. In anembodiment, the lights fraction can comprise less than about 10 wt. %,alternatively less than about 5 wt. %, alternatively less than about 4wt. %, alternatively at less than about 3 wt. %, alternatively less thanabout 2 wt. %, alternatively less than about 1 wt. % C₁₀₊ compounds,based on the total weight of the lights fraction.

In an embodiment, the C⁹⁻ monoolefins can comprise, can consistessentially of, or can be, a C₇ monoolefin, a C₈ monoolefin, a C₉monoolefin, or combinations thereof; alternatively, a C₇ monoolefin;alternatively, a C₈ monoolefin; or alternatively, a C₉ monoolefin. Insome embodiments, the C⁹⁻ monoolefins can comprise, can consistessentially of, or can be, a C₈ monoolefin (e.g., 1-octene).

In an embodiment, the C⁹⁻ mercaptans can comprise, can consistessentially of, or can be, a C₇ mercaptan, a C₈ mercaptan, a C₉mercaptan, or combinations thereof; alternatively, a C₇ mercaptan;alternatively, a C₈ mercaptan; or alternatively, a C₉ mercaptan. In someembodiments, the C⁹⁻ mercaptans can comprise, can consist essentiallyof, or can be, a C₈ mercaptan.

Following removal of the lights (for example, via flashing), a combinedintermediate and heavy fraction (i.e., C₁₀₊ compounds sometimes referredto as a kettle product) can remain, and the combined intermediate andheavy fraction can be used “as is” or can be further processed, forexample separated or split into separate intermediate and heavyfractions (and said separate intermediate and heavy fractions can besubsequently recombined in various blends and associated blend ratios),as described in more detail herein. In an embodiment, a combinedintermediate and heavy fraction (i.e., C₁₀₊ compounds) formed by removalof the lights fraction from the crude composition can comprise less thanabout 15 wt. %, alternatively less than about 10 wt. %, alternativelyless than about 9 wt. %, alternatively less than about 8 wt. %,alternatively less than about 7 wt. %, alternatively less than about 6wt. %, alternatively less than about 5 wt. %, alternatively less thanabout 4 wt. %, alternatively less than about 3 wt. %, alternatively lessthan about 2 wt. %, alternatively less than about 1 wt. % C⁹⁻ products,based on the total weight of the combined intermediate and heavyfraction (i.e., C₁₀₊ compounds).

In an embodiment, a combined intermediate and heavy fraction (i.e., C₁₀₊compounds) can comprise (A) at least about 50 wt. %, alternatively atleast about 60 wt. %, alternatively at least about 70 wt. %,alternatively at least about 80 wt. %, alternatively at least about 90wt. %, alternatively at least about 95 wt. %, or alternatively at leastabout 99 wt. % mercaptans; wherein at least about 50 wt. %,alternatively at least about 60 wt. %, alternatively at least about 70wt. %, alternatively at least about 75 wt. %. alternatively at leastabout 80 wt. %, or alternatively at least about 85 wt. % of themercaptans can be branched C₁₀ mercaptans selected from the groupconsisting of 5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof; and (B) at least about 10 wt. %, alternatively atleast about 15 wt. %, alternatively at least about 20 wt. %,alternatively at least about 25 wt. % sulfides, or alternatively atleast about 30 wt. % sulfides; wherein at least about 50 wt. %,alternatively at least about 60 wt. %, alternatively at least about 70wt. %, alternatively at least about 75 wt. %, alternatively at leastabout 80 wt. %, or alternatively at least about 85 wt. % of the sulfidescan be branched C₂₀ sulfides represented by structure R¹—S—R², whereinboth R¹ and R² can each independently be a functional group derived froman olefin, wherein the olefin comprises 5-methyl-1-nonene (representedby Structure I), 3-propyl-1-heptene (represented by Structure J),4-ethyl-1-octene (represented by Structure K), 2-butyl-1-hexene(represented by Structure L), or combinations thereof.

In an embodiment, the crude composition can be flashed to remove alights fraction as described herein to produce a combined intermediateand heavy fraction (i.e., C₁₀₊ compounds) comprising: (A) at least about25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 wt. % C₁₀ branchedmercaptans selected from the group consisting of5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof; and (B) at least about 5 wt. %, alternatively atleast about 10 wt. %, alternatively at least about 15 wt. %,alternatively at least about 20 wt. %, alternatively at least about 25wt. %, or alternatively at least about 30 wt. % branched C₂₀ sulfidesrepresented by structure R¹—S—R², wherein both R¹ and R² can eachindependently be a functional group derived from an olefin, wherein theolefin comprises 5-methyl-1-nonene (represented by Structure I),3-propyl-1-heptene (represented by Structure J), 4-ethyl-1-octene(represented by Structure K), 2-butyl-1-hexene (represented by StructureL), or combinations thereof.

In an embodiment, the crude composition can be flashed to remove alights fraction as described herein to produce a combined intermediateand heavy fraction (i.e., C₁₀₊ compounds) comprising: (A) from at leastabout 50 wt. % to at least about 90 wt. %, alternatively from at leastabout 55 wt. % to at least about 85 wt. %, or alternatively from atleast about 60 wt. % to at least about 80 wt. % mercaptans, wherein atleast about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 75wt. %, alternatively at least about 80 wt. %, or alternatively at leastabout 85 wt. % of the mercaptans can be branched C₁₀ mercaptans selectedfrom the group consisting of 5-methyl-1-mercapto-nonane (represented byStructure A), 3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof; and (B) from at least about 10 wt. % to at leastabout 30 wt. %, alternatively from at least about 10 wt. % to at leastabout 25 wt. %, alternatively from at least about 12.5 wt. % to at leastabout 22.5 wt. %, or alternatively from at least about 15 wt. % to atleast about 20 wt. % sulfides; wherein at least about 50 wt. %,alternatively at least about 60 wt. %, alternatively at least about 70wt. %, alternatively at least about 75 wt. %, alternatively at leastabout 80 wt. %, or alternatively at least about 85 wt. % of the sulfidescan be branched C₂₀ sulfides represented by structure R¹—S—R², whereinboth R¹ and R² can each independently be a functional group derived froman olefin, wherein the olefin comprises 5-methyl-1-nonene (representedby Structure I), 3-propyl-1-heptene (represented by Structure J),4-ethyl-1-octene (represented by Structure K), 2-butyl-1-hexene(represented by Structure L), or combinations thereof.

In an embodiment, the crude composition can be flashed to remove alights fraction and subsequently further separated to produce anintermediate fraction and a heavies fraction. The intermediate fractionand the heavies fractions can then be optionally further processed(e.g., polished) and mixed in any appropriate ratio to produce a blendedcomposition comprising: (A) at least about 25 wt. %, alternatively atleast about 30 wt. %, alternatively at least about 40 wt. %,alternatively at least about 50 wt. %, alternatively at least about 80wt. %, or alternatively at least about 90 wt. % C₁₀ mercaptans (e.g.,branched C₁₀ mercaptans) selected from the group consisting of5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof; (B) at least about 5 wt. %, alternatively at leastabout 10 wt. %, alternatively at least about 15 wt. %, alternatively atleast about 20 wt. %, alternatively at least about 25 wt. %, oralternatively at least about 30 wt. % C₂₀ sulfides (e.g., branched C₂₀sulfides) represented by structure R¹—S—R², wherein R¹ and R² can eachindependently be a functional group derived from an olefin, wherein theolefin comprises 5-methyl-1-nonene (represented by Structure I),3-propyl-1-heptene (represented by Structure J), 4-ethyl-1-octene(represented by Structure K), 2-butyl-1-hexene (represented by StructureL), or combinations thereof; and one or more of the following components(C)-(I): (C) less than about 5 wt. %, alternatively less than about 4wt. %, alternatively less than about 3 wt. %, alternatively less thanabout 2 wt. %, or alternatively less than about 1 wt. % C₈ mercaptans;(D) less than about 15 wt. %, alternatively less than about 10 wt. %, oralternatively less than about 5 wt. % C₁₂ mercaptans; (E) less thanabout 15 wt. %, alternatively less than about 10 wt. %, or alternativelyless than about 5 wt. % C₁₄ mercaptans; (F) less than about 5 wt. %,alternatively less than about 4 wt. %, alternatively less than about 3wt. %, alternatively less than about 2 wt. %, or alternatively less thanabout 1 wt. % C₁₆ mercaptans and/or C₁₈ mercaptans; (G) less than about1 wt. %, alternatively less than about 0.5 wt. %, alternatively lessthan about 0.4 wt. %, alternatively less than about 0.3 wt. %,alternatively less than about 0.2 wt. %, or alternatively less thanabout 0.1 wt. % C₁₆₋₃₆ sulfides represented by the structure R³—S—R⁴,wherein R³ and R⁴ are each independently a functional group derived froman olefin selected from the group consisting of C₈ monoolefins, C₁₀monoolefins, C₁₂ monoolefins, C₁₄ monoolefins, C₁₆ monoolefins, and C₁₈monoolefins, wherein R³ and R⁴ are not both branched C₁₀ monoolefins;(H) less than about 10 wt. %, alternatively less than about 5 wt. %,alternatively less than about 4 wt. %, alternatively less than about 3wt. %, alternatively less than about 2 wt. %, or alternatively less thanabout 1 wt. % unreacted C₈₋₁₈ monoolefins; and (I) less than about 10wt. %, alternatively less than about 5 wt. %, alternatively less thanabout 4 wt. %, alternatively less than about 3 wt. %, alternatively lessthan about 2 wt. %, or alternatively less than about 1 wt. % non-olefinimpurities selected from the group consisting of C₈₋₁₄ alkanes,cyclohexane, methylcyclopentane, methylcyclohexane, benzene, toluene,ethylbenzene, xylene, mesitylene, hexamethylbenzene, C₄₋₁₂ alcohols,2-ethyl-1-hexanol, and 2-ethylhexyl-2-ethylhexanoate. In variousembodiments, the blended composition can comprise varying amounts ofeach of components (C)-(I), and the presence of each component (C)-(I)and the amount thereof can be independently formulated and/orcontrolled. In various embodiments, the blended composition can comprisean amount of one or more components (C)-(I) that is greater than zero(i.e., above a detection limit associated with the component) and lessthan the upper range endpoint set forth above (e.g., component (C) ispresent in the composition in an amount greater than zero and less thanabout 5 wt. %, and so forth as set forth above).

In some embodiments, a mercaptan/sulfide composition of the typedisclosed herein can be prepared by combining at least a portion of afirst mercaptan/sulfide composition (wherein only a lights fraction hasbeen removed from the crude product to yield a combined intermediate andheavy fraction, e.g., C₁₀₊ compounds) with at least a portion of aheavies fraction comprising a sulfide composition to yield a secondmercaptan/sulfide composition, wherein a sulfide content of the secondmercaptan/sulfide composition is greater than a sulfide content of thefirst mercaptan/sulfide composition.

In an embodiment, the crude can be separated into light, intermediate,and heavy fractions by distillation, for example in a singledistillation column having a light fraction recovered as an overheadstream, an intermediate fraction (e.g., comprising branched C₁₀mercaptans) recovered as a side stream, and a heavy fraction (e.g.,comprising branched C₂₀ sulfides) recovered as a bottom stream. Inalternative embodiments, the separation can be in sequential steps suchas removal of the lights fraction in a first distillation column,followed by separation of the intermediate fraction (e.g., comprisingbranched C₁₀ mercaptans) as an overhead stream in a second distillationcolumn and the heavy fraction (e.g., comprising C₁₁₊ compounds,including branched C₂₀ sulfides) as a bottom stream of the seconddistillation column. These “rough-cut” light, intermediate, and heavystreams can be used “as is” or they can be further processed (e.g.,further refined or polished, for example by additional distillation orother separation techniques to produce “fine-cuts”) and/or blended toobtain a variety of products that are salable or otherwise available fora variety of end uses such as mining ore collector compositions or chaintransfer agents. For example, a variety of mercaptan compositions,sulfide compositions, and mixed mercaptan/sulfide compositions can beproduced of the type disclosed in more detail herein.

In an embodiment, an intermediate fraction can comprise at least about25 wt. %, alternatively at least about 30 wt. %, alternatively at leastabout 40 wt. %, alternatively at least about 50 wt. % branched C₁₀mercaptans, alternatively at least about 75 wt. % branched C₁₀mercaptans, or alternatively at least about 85 wt. % branched C₁₀mercaptans. In such embodiment, the branched C₁₀ mercaptans can beselected from the group consisting of 5-methyl-1-mercapto-nonane(represented by Structure A), 3-propyl-1-mercapto-heptane (representedby Structure B), 4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In an embodiment, the heavy fraction can comprise at least about 5, 10,15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 wt. %,branched C₂₀ sulfides represented by structure R¹—S—R², wherein both R¹and R² are each independently a branched C₁₀ alkyl group derived fromthe branched C₁₀ monoolefin, and wherein the branched C₁₀ alkyl group isselected from the group consisting of

wherein * designates the attachment point to the S atom of the branchedC₂₀ sulfide.

In an embodiment, a mercaptan composition can comprise mercaptans,wherein at least a portion of the mercaptans comprise C₁₀ mercaptans,and wherein at least a portion of the C₁₀ mercaptans comprise branchedC₁₀ mercaptans. In an embodiment, the branched C₁₀ mercaptans cancomprise 5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), or combinationsthereof.

For purposes of the disclosure herein, branched C₁₀ mercaptans refer tomercaptans (or thiols) that are characterized by the general formulaR—SH, wherein R is a branched alkyl group (as opposed to a linear alkylgroup), i.e., an alkyl group substituted with alkyl substituents; andwherein R has a total of 10 carbon atoms. Further, for purposes of thedisclosure herein, a composition comprising mercaptans, wherein at leasta portion of the mercaptans are branched C₁₀ mercaptans (e.g.,5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), or combinationsthereof), can also be referred to as a “branched C₁₀ mercaptancomposition.” In an embodiment, the mercaptan composition can compriseany suitable amount of branched C₁₀ mercaptans.

In an embodiment, the C₁₀ mercaptans can further comprise non-branchedC₁₀ mercaptans, such as for example 1-mercapto-decane (represented byStructure M), 4-mercapto-decane (represented by Structure N),5-mercapto-decane (represented by Structure 0), 2-mercapto-decane(represented by Structure P), or combinations thereof.

In some embodiments, a mercaptan composition can comprise mercaptans,wherein at least about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 80wt. %, alternatively at least about 90 wt. %, alternatively at leastabout 95 wt. %, or alternatively at least about 99 wt. % of themercaptans can be branched C₁₀ mercaptans selected from the groupconsisting of 5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In other embodiments, a mercaptan composition can comprise at leastabout 1 wt. %, alternatively at least about 5 wt. %, alternatively atleast about 10 wt. %, alternatively at least about 20 wt. %,alternatively at least about 30 wt. %, alternatively at least about 40wt. %, alternatively at least about 50 wt. %, alternatively at leastabout 60 wt. %, alternatively at least about 70 wt. %, alternatively atleast about 80 wt. %, alternatively at least about 90 wt. %,alternatively at least about 95 wt. %, or alternatively at least about99 wt. % mercaptans, wherein at least a portion of the mercaptans can bebranched C₁₀ mercaptans selected from the group consisting of5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In yet other embodiments, a mercaptan composition can comprise at leastabout 50 wt. %, alternatively at least about 60 wt. %, alternatively atleast about 70 wt. %, alternatively at least about 80 wt. %,alternatively at least about 90 wt. %, alternatively at least about 95wt. %, or alternatively at least about 99 wt. % mercaptans; wherein atleast about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 75wt. %, alternatively at least about 80 wt. %, or alternatively at least85 wt. % of the mercaptans can be branched C₁₀ mercaptans selected fromthe group consisting of 5-methyl-1-mercapto-nonane (represented byStructure A), 3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In yet other embodiments, a mercaptan composition can comprise at leastabout 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt. % mercaptans;wherein at least about 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80,85, 90, 95, or 99 wt. % of the mercaptans can be branched C₁₀ mercaptansselected from the group consisting of 5-methyl-1-mercapto-nonane(represented by Structure A), 3-propyl-1-mercapto-heptane (representedby Structure B), 4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In still yet other embodiments, a mercaptan composition can comprisefrom at least about 50 wt. % to at least about 90 wt. %, alternativelyfrom at least about 55 wt. % to at least about 85 wt. %, oralternatively from at least about 60 wt. % to at least about 80 wt. %mercaptans, wherein at least about 50 wt. %, alternatively at leastabout 60 wt. %, alternatively at least about 70 wt. %, alternatively atleast about 75 wt. %, alternatively at least about 80 wt. %, oralternatively at least about 85 wt. % of the mercaptans can be branchedC₁₀ mercaptans selected from the group consisting of5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In still yet other embodiments, a mercaptan composition can consist ofor consist essentially of branched C₁₀ mercaptans selected from thegroup consisting of 5-methyl-1-mercapto-nonane (represented by StructureA), 3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In still yet other embodiments, a mercaptan composition can comprise atleast about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70,75, 80, 85, 90, 95, or 99 wt. % branched C₁₀ mercaptans selected fromthe group consisting of 5-methyl-1-mercapto-nonane (represented byStructure A), 3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In still yet other embodiments, a composition can comprise mercaptans,wherein at least about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt.% of the mercaptans are branched C₁₀ mercaptans selected from the groupconsisting of 5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In an embodiment, a sulfide composition can comprise sulfides, whereinat least a portion of the sulfides comprise C₂₀ sulfides, and wherein atleast a portion of the C₂₀ sulfides comprise branched C₂₀ sulfidesrepresented by structure R¹—S—R², wherein R¹ and R² can eachindependently be an alkyl group, and wherein at least a portion of thealkyl groups comprises a branched C₁₀ alkyl group. In an embodiment, thealkyl group (e.g., a branched C₁₀ alkyl group as R¹, R²) can comprise afunctional group derived from an olefin, wherein the olefin comprises5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

For purposes of the disclosure herein a sulfide will be referred to bythe total number of carbon atoms (as opposed to the number of carbons ofonly one of the alkyl groups present in a dialkyl sulfide). For example,a H₂₁C₁₀—S—C₁₀H₂₁ sulfide will be referred to as a C₂₀ sulfide (ratherthan a C₁₀ sulfide). For purposes of the disclosure herein, branched C₂₀sulfides refer to sulfides (or thioethers) that are characterized by thegeneral formula R¹—S—R², wherein both R¹ and R² are each independently abranched C₁₀ alkyl group (as opposed to a linear alkyl group), i.e., analkyl group substituted with alkyl substituents. Stated alternatively,branched C₂₀ sulfides refer to sulfides wherein both R¹ and R² arebranched C₁₀ alkyl groups, wherein R¹ and R² can be the same ordifferent. Further, for purposes of the disclosure herein, a compositioncomprising sulfides, wherein at least a portion of the sulfides arebranched C₂₀ sulfides represented by structure R¹—S—R², wherein both R¹and R² are each independently an alkyl group, wherein at least a portionof the alkyl group comprises a branched C₁₀ alkyl group (e.g., afunctional group derived from an olefin, and wherein the olefincomprises 5-methyl-1-nonene (represented by Structure I),3-propyl-1-heptene (represented by Structure J), 4-ethyl-1-octene(represented by Structure K), 2-butyl-1-hexene (represented by StructureL), or combinations thereof), can also be referred to as a “branched C₂₀sulfide composition.” In an embodiment, the sulfide composition cancomprise any suitable amount of branched C₂₀ sulfides.

In an embodiment, a sulfide composition can comprise sulfides, whereinat least a portion of the sulfides comprise C₂₀ sulfides, and wherein atleast a portion of the C₂₀ sulfides comprise branched C₂₀ sulfidesrepresented by structure R¹—S—R², wherein both R¹ and R² can eachindependently be a branched C₁₀ alkyl group derived from a branched C₁₀monoolefin, and wherein the branched C₁₀ alkyl group is selected fromthe group consisting of

wherein * designates the attachment point to the S atom of the branchedC₂₀ sulfide. In an embodiment, the branched C₁₀ monoolefin can comprises5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof. Generally, a monoolefin is a linear or branched aliphatichydrocarbon olefin that has one and only one carbon-carbon double bond.Generally, a C_(n) monoolefin is a linear or branched aliphatichydrocarbon olefin that has n and only n carbon atoms, and one and onlyone carbon-carbon double bond. A C₁₀ monoolefin is a linear or branchedaliphatic hydrocarbon olefin that has ten and only ten carbon atoms, andone and only one carbon-carbon double bond. A branched C₁₀ monoolefin isa branched aliphatic hydrocarbon olefin that has ten and only ten carbonatoms, and one and only one carbon-carbon double bond.

In an embodiment, the C₂₀ sulfides can further comprise non-branched C₂₀sulfides and/or partially branched C₂₀ sulfides represented by structureR¹—S—R², wherein both R¹ and R² (in the case of non-branched C₂₀sulfides) or one of the R¹ and R² (in the case of partially-branched C₂₀sulfides) can be a linear C₁₀ alkyl group derived from a linear C₁₀monoolefin, such as for example 4-decene (represented by Structure Q),5-decene (represented by Structure R), 1-decene (represented byStructure S), or combinations thereof.

For purposes of the disclosure herein, the non-branched C₂₀ sulfidesrepresented by structure R¹—S—R² are the sulfides wherein both R¹ and R²are each independently a linear C₁₀ alkyl group derived from a linearC₁₀ monoolefin. Further, for purposes of the disclosure herein, thepartially branched C₂₀ sulfides represented by structure R¹—S—R² are thesulfides wherein one of the R¹ and R² is a linear C₁₀ alkyl groupderived from a linear C₁₀ monoolefin, while the other one of the R¹ andR² is a branched C₁₀ alkyl group derived from a branched C₁₀ monoolefinas described herein.

In some embodiments, a sulfide composition can comprise sulfides,wherein at least about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 80wt. %, alternatively at least about 90 wt. %, alternatively at leastabout 95 wt. %, or alternatively at least about 99 wt. % of the sulfidescan be branched C₂₀ sulfides represented by structure R¹—S—R², whereinboth R¹ and R² can each independently be a functional group derived froman olefin, wherein the olefin comprises 5-methyl-1-nonene (representedby Structure I), 3-propyl-1-heptene (represented by Structure J),4-ethyl-1-octene (represented by Structure K), 2-butyl-1-hexene(represented by Structure L), or combinations thereof.

In other embodiments, a sulfide composition can comprise at least about1 wt. %, alternatively at least about 5 wt. %, alternatively at leastabout 10 wt. %, alternatively at least about 20 wt. %, alternatively atleast about 30 wt. %, alternatively at least about 40 wt. %,alternatively at least about 50 wt. %, alternatively at least about 60wt. %, alternatively at least about 70 wt. %, alternatively at leastabout 80 wt. %, alternatively at least about 90 wt. %, alternatively atleast about 95 wt. %, or alternatively at least about 99 wt. % sulfides,wherein at least a portion of the sulfides can be branched C₂₀ sulfidesrepresented by structure R¹—S—R², wherein both R¹ and R² can eachindependently be a functional group derived from an olefin, wherein theolefin comprises 5-methyl-1-nonene (represented by Structure I),3-propyl-1-heptene (represented by Structure J), 4-ethyl-1-octene(represented by Structure K), 2-butyl-1-hexene (represented by StructureL), or combinations thereof.

In other embodiments, a sulfide composition can comprise at least about1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85,90, 95, or 99 wt. %, sulfides, wherein at least about 1, 5, 10, 15, 20,25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt. %of the sulfides can be branched C₂₀ sulfides represented by structureR¹—S—R², wherein both R¹ and R² can each independently be a functionalgroup derived from an olefin, wherein the olefin comprises5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

In yet other embodiments, a sulfide composition can comprise at leastabout 10 wt. %, alternatively at least about 15 wt. %, alternatively atleast about 20 wt. %, or alternatively at least about 25 wt. % sulfides;wherein at least about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 75wt. %, alternatively at least about 80 wt. %, or alternatively at leastabout 85 wt. % of the sulfides can be branched C₂₀ sulfides representedby structure R¹—S—R², wherein both R¹ and R² can each independently be afunctional group derived from an olefin, wherein the olefin comprises5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

In still yet other embodiments, a sulfide composition can comprise fromat least about 10 wt. % to at least about 30 wt. %, alternatively fromat least about 12.5 wt. % to at least about 22.5 wt. %, or alternativelyfrom at least about 15 wt. % to at least about 20 wt. % sulfides;wherein at least about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 75wt. %, alternatively at least about 80 wt. %, or alternatively at leastabout 85 wt. % of the sulfides can be branched C₂₀ sulfides representedby structure R¹—S—R², wherein both R¹ and R² can each independently be afunctional group derived from an olefin, wherein the olefin comprises5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

In still yet other embodiments, a sulfide composition can consist of orconsist essentially of branched C₂₀ sulfides represented by structureR¹—S—R², wherein both R¹ and R² can each independently be a functionalgroup derived from an olefin, wherein the olefin comprises5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

In still yet other embodiments, a sulfide composition can comprise atleast about 5 wt. %, alternatively at least about 10 wt. %,alternatively at least about 15 wt. %, or alternatively at least about20 wt. % C₂₀ sulfides (e.g., branched C₂₀ sulfides) represented bystructure R¹—S—R², wherein both R¹ and R² can each independently be afunctional group derived from an olefin, wherein the olefin comprises5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

In still yet other embodiments, a sulfide composition comprises at leastabout 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80,85, 90, 95, or 99 wt. % branched C₂₀ sulfides represented by thestructure R¹—S—R², wherein R¹ and R² are each independently a functionalgroup derived from an olefin, wherein the olefin comprises5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

In an embodiment, a mercaptan/sulfide composition can comprise one ormore mercaptans and one or more sulfides of the type disclosed herein.For purposes of the disclosure herein, a composition comprising (i)mercaptans, wherein at least a portion of the mercaptans are branchedC₁₀ mercaptans, and (ii) sulfides, wherein at least a portion of thesulfides are branched C₂₀ sulfides, can also be referred to as a“branched C₁₀ mercaptan/C₂₀ sulfide composition.” In an embodiment, themercaptan/sulfide composition can comprise any suitable amount ofbranched C₁₀ mercaptans, and any suitable amount of branched C₂₀sulfides.

In an embodiment, a mercaptan/sulfide composition can comprise (A) atleast about 1 wt. %, alternatively at least about 5 wt. %, alternativelyat least about 10 wt. %, alternatively at least about 20 wt. %,alternatively at least about 30 wt. %, alternatively at least about 40wt. %, alternatively at least about 50 wt. %, alternatively at leastabout 60 wt. %, alternatively at least about 70 wt. %, alternatively atleast about 80 wt. %, alternatively at least about 90 wt. %,alternatively at least about 95 wt. %, or alternatively at least about99 wt. % mercaptans, wherein at least a portion of the mercaptans can bebranched C₁₀ mercaptans selected from the group consisting of5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof; and (B) at least about 1 wt. %, alternatively atleast about 5 wt. %, alternatively at least about 10 wt. %,alternatively at least about 20 wt. %, alternatively at least about 30wt. %, alternatively at least about 40 wt. %, alternatively at leastabout 50 wt. %, alternatively at least about 60 wt. %, alternatively atleast about 70 wt. %, alternatively at least about 80 wt. %,alternatively at least about 90 wt. %, alternatively at least about 95wt. %, or alternatively at least about 99 wt. % sulfides, wherein atleast a portion of the sulfides can be branched C₂₀ sulfides representedby structure R¹—S—R², wherein both R¹ and R² can each independently be afunctional group derived from an olefin, wherein the olefin comprises5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

In an embodiment, a mercaptan/sulfide composition can comprise C₁₀mercaptans represented by the general formula R—SH and/or C₂₀ sulfidesrepresented by structure R¹—S—R² that are formed by reacting an olefinfeedstock comprising olefins with H₂S as described in more detailherein, wherein the olefins present in the olefin feedstock provide thealkyl group represented by R, R¹, and R². In such embodiments, the Rgroup of the C₁₀ mercaptans and/or the R¹ and R² groups of the C₂₀sulfides are provided by or derived from the counterpart R, R¹, and R²groups present in the olefins in the olefin feedstock. In an embodiment,R, R¹ and R² can each independently be an alkyl group, wherein at leasta portion of the alkyl groups can comprise a functional group derivedfrom an olefin, wherein the olefin is present in a feedstock (e.g., afirst feedstock as described herein) comprising a) at least about 76 mol%, alternatively at least about 78 mol %, alternatively at least about80 mol %, or alternatively at least about 82 mol % C₁₀ monoolefins; andb) at least about 1 mol %, alternatively at least about 2 mol %,alternatively at least about 3 mol %, or alternatively at least about 4mol % C₁₄ monoolefins. In such embodiment, the C₁₀ monoolefins cancomprise i) at least about 3 mol %, alternatively at least about 4 mol%, alternatively at least about 5 mol %, alternatively at least about 6mol %, alternatively at least about 7 mol %, or alternatively at leastabout 8 mol % 2-butyl-1-hexene (represented by Structure L), ii) atleast about 8 mol %, alternatively at least about 9 mol %, alternativelyat least about 10 mol %, alternatively at least about 11 mol %,alternatively at least about 12 mol %, or alternatively at least about13 mol % 3-propyl-1-heptene (represented by Structure J), iii) at leastabout 6 mol %, alternatively at least about 7 mol %, alternatively atleast about 8 mol %, alternatively at least about 9 mol %, alternativelyat least about 10 mol %, or alternatively at least about 11 mol %4-ethyl-1-octene (represented by Structure K), and iv) at least about 20mol %, alternatively at least about 22 mol %, alternatively at leastabout 24 mol %, alternatively at least about 26 mol %, alternatively atleast about 28 mol %, or alternatively at least about 30 mol %5-methyl-1-nonene (represented by Structure I). In an embodiment, theC₁₀ monoolefins can comprise from about 1 mol % to about 16 mol %,alternatively from about 2 mol % to about 15 mol %, alternatively fromabout 3 mol % to about 14 mol %, alternatively from about 4 mol % toabout 13 mol %, or alternatively from about 6 mol % to about 12 mol %4-decene and/or 5-decene. In an embodiment, the C₁₀ monoolefins cancomprise from about 0.5 mol % to about 9 mol %, alternatively from about1 mol % to about 8 mol %, alternatively from about 1.5 mol % to about 7mol %, or alternatively from about 2 mol % to about 6 mol % 1-decene.

In an embodiment, the olefin (e.g., corresponding to R, R¹ or R²)present in the olefin feedstock (e.g., a first feedstock as describedherein) can further comprise from about 0.1 mol % to about 5 mol %,alternatively from about 0.25 mol % to about 4 mol %, or alternativelyfrom about 0.5 mol % to about 3 mol % C₁₂ monoolefins. In suchembodiment, the C₁₂ monoolefins can comprise from about 54 mol % toabout 74 mol %, alternatively from about 56 mol % to about 72 mol %,alternatively from about 58 mol % to about 70 mol %, or alternativelyfrom about 60 mol % to about 68 mol % 1-dodecene.

In an embodiment, the olefin (e.g., corresponding to R, R¹ or R²)present in the olefin feedstock (e.g., a first feedstock as describedherein) can further comprise from about 0.1 mol % to about 5 mol %,alternatively from about 0.25 mol % to about 4 mol %, or alternativelyfrom about 0.5 mol % to about 3 mol % C₈ monoolefins. In suchembodiment, the C₈ monoolefins can comprise at least about 95 mol %,alternatively at least about 96 mol %, alternatively at least about 97mol %, alternatively at least about 98 mol %, or alternatively at leastabout 99 mol % 1-octene.

In an embodiment, the olefin (e.g., corresponding to R, R¹ or R²)present in the olefin feedstock (e.g., a first feedstock as describedherein) can further comprise from about 0.05 mol % to about 2 mol %,alternatively from about 0.04 mol % to about 1.5 mol %, alternativelyfrom about 0.06 mol % to about 1.25 mol %, alternatively from about 0.08mol % to about 1 mol %, or alternatively from about 0.1 mol % to about0.75 mol % C₁₆ monoolefins and/or C₁₈ monoolefins.

In an embodiment where the R group of the C₁₀ mercaptans and/or the R¹and R² groups of the C₂₀ sulfides are provided by or derived from thecounterpart R, R¹, and R² groups present in the olefins in the olefinfeedstock (e.g., a first feedstock obtained from a 1-hexene process asdescribed herein), the resultant mercaptan/sulfide composition can be acrude composition that can be further separated and refined into othercompositions as described herein.

In an embodiment, mercaptan compositions, sulfide compositions, and/ormercaptan/sulfide compositions as disclosed herein advantageouslydisplay improvements in one or more composition characteristics whencompared to otherwise similar compositions lacking branched C₁₀mercaptans.

In an embodiment, a mercaptan composition and/or a mercaptan/sulfidecomposition comprising equal to or greater than about 25 wt. % C₁₀branched mercaptans as disclosed herein can advantageously have an odorless unpleasant and less offensive than an odor of an otherwise similarcomposition comprising equal to or greater than about 25 wt. % n-decylmercaptan, as perceived by equal to or greater than about 51% of humansubjects exposed to the odor of each composition.

In an embodiment, a mercaptan composition and/or a mercaptan/sulfidecomposition comprising equal to or greater than about 25 wt. % C₁₀branched mercaptans as disclosed herein can advantageously have an odorless unpleasant than an odor of an otherwise similar compositioncomprising equal to or greater than about 25 wt. % n-dodecyl mercaptanand/or tert-dodecyl mercaptan, as perceived by equal to or greater thanabout 51% of human subjects exposed to the odor of each composition.Additional advantages of the mercaptan compositions, sulfidecompositions, and/or mercaptan/sulfide compositions and processes ofproducing same as disclosed herein can be apparent to one of skill inthe art viewing this disclosure.

Mining Collector Compositions

Alternative embodiments of the invention also are directed to collectorcompositions (such as mining chemical collector compositions) forrecovering one or more metals from mined ore wherein the collectorcompositions comprise any of the branched C₁₀ mercaptan and/or any ofthe branched C₂₀ sulfide compositions in any of the amounts describedherein and above. Unexpectedly, it was found that the branched C₁₀mercaptan and/or branched C₂₀ sulfide compositions disclosed hereinaboveare very effective at removing metals from mining ores. Moreover, it wasunexpectedly found that compositions comprising branched C₁₀ mercaptansalone or in combination with the branched C₂₀ sulfides do not have anundesirable or offensive odor often associated with other mercaptanmining collectors (e.g., tert-dodecyl mercaptans and n-dodecylmercaptans).

The branched C₁₀ mercaptan and/or branched C₂₀ sulfide compositions inthe collector composition can collectively be referred to as the“sulfur-containing compounds” of the collector composition.

In various embodiments, the sulfur-containing compounds in the collectorcomposition can be described as mercaptan compositions (e.g., acomposition comprising one or more branched C₁₀ mercaptans); sulfidecompositions (e.g., a composition comprising one or more branched C₂₀sulfides); compositions comprising both mercaptans (e.g., branched C₁₀mercaptans) and sulfides (e.g., branched C₂₀ sulfides) and referred toas mercaptan/sulfide compositions; a crude composition (e.g., a crudereaction product as described herein); an intermediate fraction; a heavyfraction; a branched C₁₀ mercaptan composition; a branched C₂₀ sulfidecomposition; a branched C₁₀ mercaptan/C₂₀ sulfide composition; orcombinations thereof, as each of these terms is defined, described, andotherwise used herein.

In an embodiment, the sulfur-containing compounds of the miningcollector composition can comprise C₁₀ mercaptan compounds, wherein atleast 50 wt. %, alternatively at least 60 wt. %, alternatively at least70 wt. %, alternatively at least 80 wt. %, alternatively at least 85 wt.%, alternatively at least 90 wt. %, alternatively at least 95 wt. %, oralternatively at least 99 wt. % of the C₁₀ mercaptan compounds arebranched, and wherein the branched C₁₀ mercaptans are selected from thegroup consisting of 5-methyl-1-mercapto-nonane (represented by StructureA), 3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In an embodiment, the sulfur-containing compounds of the miningcollector compositions can consist essentially of C₁₀ mercaptancompounds, wherein the composition comprises (A) at least 85 wt. %,alternatively at least 90 wt. %, alternatively at least 95 wt. %,alternatively at least 99 wt. %, alternatively at least 99.9 wt. % C₁₀mercaptans, and wherein at least 50 wt. % of the C₁₀ mercaptans arebranched mercaptans as previously described herein. In an alternativeembodiment, the mining collector can consist essentially of C₁₀mercaptan compounds wherein a least 50 wt. % of the C₁₀ mercaptans arebranched mercaptans as previously described herein; (B) less than about5 wt. %, alternatively less than about 4 wt. %, alternatively less thanabout 3 wt. %, alternatively less than about 2 wt. %, or alternativelyless than about 1 wt. % C₈ mercaptans; (C) less than about 15 wt. %,alternatively less than about 10 wt. %, alternatively less than about 5wt. %, or alternatively less than about 1 wt. % C₁₂ mercaptans; (D) lessthan about 15 wt. %, alternatively less than about 10 wt. %,alternatively less than about 5 wt. %, or alternatively less than about1 wt. % C₁₄ mercaptans; (F) less than about 5 wt. %, alternatively lessthan about 4 wt. %, alternatively less than about 3 wt. %, alternativelyless than about 2 wt. %, or alternatively less than about 1 wt. % C₁₆mercaptans and/or C₁₈ mercaptans; (E) less than about 1 wt. %,alternatively less than about 0.5 wt. %, alternatively less than about0.4 wt. %, alternatively less than about 0.3 wt. %, alternatively lessthan about 0.2 wt. %, or alternatively less than about 0.1 wt. % C₁₆₋₃₆sulfides represented by the structure R³—S—R⁴, wherein R³ and R⁴ areeach independently a functional group derived from an olefin selectedfrom the group consisting of C₈ monoolefins, C₁₀ monoolefins, C₁₂monoolefins, C₁₄ monoolefins, C₁₆ monoolefins, and C₁₈ monoolefins,wherein R³ and R⁴ are not both branched C₁₀ monoolefins; (F) less thanabout 10 wt. %, alternatively less than about 5 wt. %, alternativelyless than about 4 wt. %, alternatively less than about 3 wt. %,alternatively less than about 2 wt. %, or alternatively less than about1 wt. % unreacted C₈₋₁₈ monoolefins; and (G) less than about 10 wt. %,alternatively less than about 5 wt. %, alternatively less than about 4wt. %, alternatively less than about 3 wt. %, alternatively less thanabout 2 wt. %, or alternatively less than about 1 wt. % non-olefincomponents selected from the group consisting of C₈₋₁₄ alkanes,cyclohexane, methylcyclopentane, methylcyclohexane, benzene, toluene,ethylbenzene, xylene, mesitylene, hexamethylbenzene, C₄₋₁₂ alcohols,2-ethyl-1-hexanol, and 2-ethylhexyl-2-ethylhexanoate.

In an alternative embodiment, the sulfur containing compounds of themining collector compositions comprise both C₁₀ mercaptans and C₂₀sulfides, wherein (A) at least 50 wt. %, alternatively at least 60 wt.%, alternatively at least 70 wt. %, alternatively at least 80 wt. %,alternatively at least 85 wt. %, alternatively at least 90 wt. %,alternatively at least 95 wt. %, or alternatively at least 99 wt. % ofthe C₁₀ mercaptan compounds are branched, wherein the branched C₁₀mercaptans are selected from the group consisting of5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof; and (B) at least 50 wt. %, alternatively at least60 wt. %, alternatively at least 70 wt. %, alternatively at least 80 wt.%, alternatively at least 85 wt. %, alternatively at least 90 wt. %,alternatively at least 95 wt. %, or alternatively at least 99 wt. % ofthe C₂₀ sulfides are branched C₂₀ sulfides of the type and structure aspreviously described herein.

In an alternative embodiment, the sulfur containing compounds of themining collector composition comprise both C₁₀ mercaptans and C₂₀sulfides, wherein (A) the C₂₀ sulfides comprise at least 20 wt. %,alternatively at least 30 wt. %, alternatively at least 40 wt. %,alternatively at least 50 wt. %, alternatively at least 60 wt. %,alternatively at least 70 wt. %, alternatively at least 75 wt. %, oralternatively equal to or less than 80 wt. % of the total composition;(B) the C₂₀ sulfides comprise branched C₂₀ sulfides of the type andstructure as previously described herein; and (C) the total compositioncomprises less than about 5 wt. %, alternatively less than about 4 wt.%, alternatively less than about 3 wt. %, alternatively less than about2 wt. %, or alternatively less than about 1 wt. % C₈ mercaptans; lessthan about 10 wt. %, alternatively less than about 5 wt. %,alternatively less than about 4 wt. %, alternatively less than about 3wt. %, alternatively less than about 2 wt. %, or alternatively less thanabout 1 wt. % unreacted C₈₋₁₈ monoolefins; and less than about 10 wt. %,alternatively less than about 5 wt. %, alternatively less than about 4wt. %, alternatively less than about 3 wt. %, alternatively less thanabout 2 wt. %, or alternatively less than about 1 wt. % non-olefincomponents selected from the group consisting of C₈₋₁₄ alkanes,cyclohexane, methylcyclopentane, methylcyclohexane, benzene, toluene,ethylbenzene, xylene, mesitylene, hexamethylbenzene, C₄₋₁₂ alcohols,2-ethyl-1-hexanol, and 2-ethylhexyl-2-ethylhexanoate.

In a preferred embodiment, the sulfur containing compounds of the miningcollector compositions comprise both C₁₀ mercaptans and C₂₀ sulfides,wherein (A) the C₂₀ sulfides comprise between about greater than orequal to 20 wt. % and less than or equal to about 80 wt. % of the totalcomposition; (B) the C₂₀ sulfides comprise branched C₂₀ sulfides of thetype and structure as previously described herein; and (C) the totalcomposition comprises less than about 5 wt. %, alternatively less thanabout 4 wt. %, alternatively less than about 3 wt. %, alternatively lessthan about 2 wt. %, or alternatively less than about 1 wt. % C₈mercaptans; less than about 10 wt. %, alternatively less than about 5wt. %, alternatively less than about 4 wt. %, alternatively less thanabout 3 wt. %, alternatively less than about 2 wt. %, or alternativelyless than about 1 wt. % unreacted C₈₋₁₈ monoolefins; and less than about10 wt. %, alternatively less than about 5 wt. %, alternatively less thanabout 4 wt. %, alternatively less than about 3 wt. %, alternatively lessthan about 2 wt. %, or alternatively less than about 1 wt. % non-olefincomponents selected from the group consisting of C₈₋₁₄ alkanes,cyclohexane, methylcyclopentane, methylcyclohexane, benzene, toluene,ethylbenzene, xylene, mesitylene, hexamethylbenzene, C₄₋₁₂ alcohols,2-ethyl-1-hexanol, and 2-ethylhexyl-2-ethylhexanoate.

While not wishing to be limited by theory, as described in thisdisclosure and as known by one of ordinary skill in the art, these andother specific compositions can be obtained any number of ways includingbut not limited to (A) removing H₂S and distilling the light compoundsfrom the crude reaction product or (B) separating the light fraction,the C₁₀ mercaptans, the intermediate fraction and the heavy fraction ofthe crude reaction mixture in any order or by any means to produce twoor more partially purified fractions and then blending any two or moreof the C₁₀ mercaptan fraction, the intermediate fraction, and the heavyfraction to produce the desired composition. For example, the C₁₀mercaptan fraction can be blended with the heavy fraction in variousratios; alternatively, the intermediate fraction, which also comprisesthe C₁₀ mercaptans, can be blended with the heavy fraction in variousratios.

In embodiments, the sulfur-containing compounds of the collectorcompositions disclosed herein have an odor which is less unpleasantand/or less offensive than an odor of other mercaptan compounds whichinclude n-decyl mercaptans, n-dodecyl mercaptans, tert-dodecylmercaptans, or combinations thereof present in an amount of equal to orgreater than about 25 wt. % of the mercaptan compounds in an otherwisesimilar mining collector composition.

The amount of the sulfur-containing compounds present in the collectorcomposition can be less than 0.1 wt. %, alternatively less than 0.01 wt.%, or alternatively less than 0.001 wt. % based on the combined totalweight of the collector composition and the ore.

The collector composition can further include water, a pH control agent,a frothing agent, a hydrocarbon, an oily reagent, a water immiscibleliquid, or combinations thereof.

Nonlimiting examples of water include tap, distilled, well, osmosis,ground, lake, pond, and rain water. The amount of water in the collectorcomposition can be greater than 75 wt. %, greater than 95 wt. %, orgreater than 99 wt. %, and typical non-limiting ranges include from 75to 99.99 wt. %, from 95 to 99.99 wt. %, or from 99 to 99.99 wt. % water,based on the total weight of the collector composition.

Nonlimiting examples of pH control agent include lime, carbonatecompounds, the like, or combinations thereof. Suitable amounts of pHcontrol agent in the collector composition include the amounts disclosedin any of the comparative and inventive examples below.

Nonlimiting examples of frothing agents include pine oil; alcohols suchas methyl isobutyl carbinol (MIBC); polyether alcohols such as NALFLOTE®9837 and Cytec OREPREP® X-133; or combinations thereof. Suitable amountsof frothing agent in the collector composition include the amountsdisclosed in any of the comparative and inventive examples below.

Moreover, the sulfur-containing compounds disclosed herein can be usedalone or in combination with other suitable (second) collector agents ina collector composition. Thus, any of the collector compositions canfurther comprise a second collector agent, non-limiting examples ofwhich can include a xanthate, a xanthic ester, a thionocarbonate, adialkyl dithiophosphate, the like, others known in the art with the aidof this disclosure, or combinations thereof. Additionally, thesulfur-containing compounds disclosed herein can be mixed or dilutedwith other liquids, including but not limited to hydrocarbons and otherwater immiscible or oily reagents, prior to use in a collectorcomposition.

Also provided herein are flotation processes or procedures for therecovery of metals from ores. The metal can be recovered in any form,for instance, a metal-containing compound (e.g., copper sulfides,molybdenum sulfides), a metal ion, or elemental metal, as well ascombinations thereof.

One such flotation process for the recovery of a metal from an ore cancomprise contacting the ore with any of the collector compositionsdisclosed herein (or any of the sulfur-containing compounds disclosedherein). Any suitable order of contacting any components of thecollector composition with the ore can be used; and such collectorcompositions, whether solutions, slurries, blends, immiscible mixtures,and so forth, are encompassed herein. For instance, a ground ore can becontacted with, in any order, the sulfur-containing compounds disclosedherein, a frothing agent, a pH control agent, and a first amount ofwater (which can be relatively small), resulting in a slurry of the oreand a collector composition comprising the sulfur-containing compounds,the frothing agent, the pH control agent, and water. In someembodiments, a second amount of water (which can be relatively large)can be added to this slurry prior to the flotation process, resulting ina slurry of the ore in a collector composition comprising lowerconcentrations of the sulfur-containing compounds, the frothing agent,and the pH control agent. In a preferred embodiment, the ore iscontacted with the sulfur-containing compounds prior to being mixed withany water, pH control agent, or frothing agent. In yet another preferredembodiment, the ore is contacted with the sulfur-containing compoundsprior to forming any slurry. Other suitable methods and orders offorming the collector compositions, whether in the presence of the oreor not, would be readily recognized by those of skill in the art, andsuch are encompassed herein.

Embodiments of the flotation processes disclosed herein generallyinclude contacting the ore (e.g., ore particles of a desired size) withthe sulfur-containing compounds disclosed herein before, during, orafter: i) any step of the flotation processes disclosed herein, ii) anystep of a specified flotation process, and iii) any step of a flotationprocess known in the art but not specifically disclosed herein. Forexample, the sulfur-containing compounds can be contacted with an ore orore particles of a desired size: i) during grinding of the ore to adesired particle size (and optionally before, after, or with theaddition of one or more other components of the collector composition),ii) after grinding (e.g., the sulfur-containing compounds can be addedto a flotation cell containing the ore particles, and optionally before,after, or with the addition of one or more other components of thecollector composition), iii) during or after adjusting the pH of thematerial in the flotation cell (e.g., the sulfur-containing compoundscan be added to a flotation cell containing the ore particles, andoptionally before, after, or with the addition of one or more othercomponents of the collector composition), iv) between and/or duringfroth removal stages (e.g., the sulfur-containing compounds can be addedto the flotation cell, and optionally before, after, or with theaddition of one or more other components of the collector composition),v) before, during, or after any other step in a flotation process orprocedure disclosed herein, specified by a mine, and/or known in theart, vi) or combinations thereof. It is contemplated that contacting thedisclosed sulfur-containing compounds with an ore or ore particlesincludes a series of additions of the sulfur-containing compounds (aloneor in combination with one or more other components of the collectorcomposition) to a rod mill, a flotation cell, or other equipmentcontaining the ore or ore particles.

Equipment and techniques for the flotation recovery of various metalsfrom mining ores are well known to those of skill in the art and areillustrated representatively herein in the examples that follow.

Generally, the metal recovered from the ore comprises a transitionmetal, one or more Group 3-12 metals. In some embodiments, the metal cancomprise a Group 3-11 transition metal, or a Group 5-12 transitionmetal, while in other embodiments, the metal can comprise gold, silver,platinum, copper, nickel, iron, lead, zinc, molybdenum, cobalt, orchromium, as well as combinations thereof. In particular embodiments ofthis invention, the metal can comprise copper and molybdenum;alternatively, copper; or alternatively, molybdenum. In addition, othertransition metals, such as iron, can be recovered along with copperand/or molybdenum. In embodiments, the metal in the ore is in the formof a metal sulfide. The metal sulfide can comprise copper sulfide,molybdenum sulfide, or combinations thereof.

The flotation processes and collector compositions described herein arenot limited to any particular ore. However, the effectiveness of suchprocesses and compositions are particularly beneficial when the orecomprises a copper-bearing ore, a molybdenum-bearing ore, or acopper-bearing and molybdenum-bearing ore. Illustrative and non-limitingexamples of such ores include chalcopyrite, chalcocite, molybdenite, andthe like.

Any suitable amount of the collector composition and/or thesulfur-containing compounds can be used in the flotation recoveryprocesses or procedures. Often, but not limited thereto, thesulfur-containing compounds and the ore are contacted at a weight ratioin a range of from about 0.45 grams (0.001 lb) of the sulfur-containingcompounds per metric ton of ore to about 2200 grams (5 lb) of thesulfur-containing compounds per metric ton of ore. In an alternativeembodiment, the sulfur-containing compounds and the ore are contacted ata weight ratio in a range of from about 4.5 grams (0.01 lb) of thesulfur-containing compounds per metric ton of ore to about 450 grams (1lb) of the sulfur-containing compounds per metric ton of ore. In apreferred embodiment, the sulfur-containing compounds and the ore arecontacted at a weight ratio in a range of from about 4.5 grams (0.01 lb)of the sulfur containing compounds per metric ton of ore to about 50grams (0.1 lb) of the sulfur-containing compounds per metric ton of ore.

Unexpectedly, the sulfur-containing compounds disclosed herein, and anyresultant collector compositions containing the sulfur-containingcompounds, have high recovery rates of certain transition metals.Recovery is defined as the amount (reported as a weight percentage) ofthe metal that is recovered after the flotation procedure compared tothe amount of metal in the original ore sample. For example, the %recovery of copper in the flotation process can be at least about 75 wt.%, at least about 80 wt. %, at least about 85 wt. %, or at least about90 wt. %, and often as high as 95 wt. %-98 wt. %. Similarly, the %recovery of molybdenum in the flotation process can be at least about 60wt. %, at least about 65 wt. %, at least about 80 wt. %, at least about85 wt. %, or at least about 90 wt. %, and often as high as 92 wt. %-97wt. %. Grade is defined as the amount (reported as a weight percentage)of a particular metal in the ore concentrate, where the ore concentrateis the product recovered from the flotation procedure.

Furthermore and surprisingly, in some embodiments, the % recovery ofcopper, the % recovery of molybdenum, or the % recovery of copper andmolybdenum of the disclosed sulfur-containing compounds, can be theabout the same as or greater than that of a mine standard, under thesame flotation conditions. As would be recognized by those of skill inthe art, a “mine standard” is the prevailing collector compositioncurrently being used for a given ore and/or desired transition metal.Mine standards are discussed in greater detail in the examples thatfollow.

Additionally or alternatively, the % recovery of copper, the % recoveryof molybdenum, or the % recovery of copper and molybdenum of thedisclosed sulfur-containing compounds, can be about the same as orgreater than that of a mining collector composition containing TDDM(tertiary dodecyl mercaptan) or NDDM (n-dodecyl mercaptan), under thesame flotation conditions. Thus, in some instances, thesulfur-containing compounds disclosed herein are superior to TDDM and/orNDDM.

Additionally or alternatively, the % recovery of copper, the % recoveryof molybdenum, or the % recovery of copper and molybdenum of thedisclosed sulfur-containing compounds, can be about the same as orgreater than that of a mining collector composition using linear(unbranched) n-decyl mercaptans, linear (unbranched) C₂₀ sulfides, orboth linear (unbranched) n-decyl mercaptans and linear (unbranched) C₂₀sulfides, under the same flotation conditions.

Production of C₁₀ Mercaptans and C₂₀ Sulfides

Hydrogen sulfide (H₂S) and a feedstock comprising branched C₁₀monoolefins were reacted in the presence of various initiating agents:UV radiation, an acid catalyst, and a hydrodesulfurization (HDS)catalyst.

Various feedstocks (e.g., olefin feedstocks) were used for reacting withH₂S to produce mercaptans and/or sulfides. More specifically, C₁₀monoolefin feedstocks obtained from 1-hexene production processes wereused as feedstocks for reacting with H₂S to produce mercaptans.Additionally, 1-decene was reacted with H₂S in the presence of a UVinitiator to produce a mixture of technical grade n-decyl mercaptan anddi-n-decyl sulfide. This composition was used for comparative examples.

Gas chromatography (GC)-mass spectrometry (MS) (GC-MS) and nuclearmagnetic resonance (NMR) spectroscopy were used for analyzing thecomposition of olefin feedstocks obtained from 1-hexene productionprocesses as well as the products of the reaction of the olefinfeedstocks with H₂S.

The compositions comprising C₁₀ monoolefins were analyzed by gas GC-MSusing a 15 m×0.25 mm×0.5 μm DB-5 column and/or a 40 m×0.1 mm×0.1 μm DB-1column to determine component identities, and standard GC using a 60m×0.32 mm×1 μm DB-1 column to determine the quantity of the componentspresent in the compositions. These compositions are measured in area %,which is substantially similar and analogous to wt. %.

Table 1 provides representative information about the typicalcomposition of such an olefin feedstock obtained from 1-hexeneproduction processes to react with H₂S to produce mercaptans.

TABLE 1 Composition of Olefin Feedstock Chemical GC Area % Normalized %cyclohexane 2.148 octene 0.036 C₈ olefins 1.17 1.24 1-octene 1.135octane 0.146 octane 0.15 0.16 ethylbenzene 1.684 3-propyl-1-heptene14.590 C₁₀ olefins 84.16 89.11 decene 0.164 4-ethyl- l-octene 13.1345-methyl- l-nonene 32.144 decene 0.647 2-butyl-1-hexene 9.960 decene0.320 4/5 decene 9.116 1-decene 4.086 decane 0.360 decane 0.36 0.382-ethyl- l-hexanol 1.379 dodecene isomers 0.448 C₁₂ olefins 1.29 1.371-dodecene 0.842 dodecane 0.182 dodecane 0.18 0.19 tetradecenes 6.710C₁₄ olefins 6.71 7.11 tetradecane 0.198 tetradecane 0.2 0.21 octadecene0.222 C₁₈ olefins 0.22 0.23 2-ethylhexyl-2- 0.069 ethylhexanoateUnknowns 0.281 Total 100.000 total olefins 94.44 99.06 Normalized toinclude only octane, decane, dodecane, tetradecane, and C₈, C₁₀, C₁₂,C₁₄, and C₁₈ olefins

As can be seen from Table 1, the total olefin content of this particularolefin feedstock (excluding the compounds that are not products of the1-hexene process) sample is 94.44 area %, and 84.16 area % of the totalfeedstock is C₁₀ olefin isomers. The C₁₀ olefins represent over 89 area% of the total olefin content when the sample is normalized to removethe compounds that are not products of the 1-hexene process.Cyclohexane, ethylbenzene, and 2-ethylhexanol can be present in theolefin feedstock as residual components of the 1-hexene oligomerizationprocess. The structures of C₁₀ isomers that can be present in the olefinfeedstock are shown in Table 2.

TABLE 2 Structures of Decene Olefins and Mercaptan Reaction ProductsDecene fraction Olefin 5-methyl-1-nonene 32.14% (38.19)

3-propyl-1- heptene 14.59% (17.33)

4-ethyl-1-octene 13.13% (15.60)

2-butyl-1-hexene 9.96% (11.83)

4/5 decene 9.12% (10.83)

1-decene 4.09% (4.86)

Decene fraction Major UV product 5-methyl-1-nonene 32.14% (38.19)

3-propyl-1- heptene 14.59% (17.33)

4-ethyl-1-octene 13.13% (15.60)

2-butyl-1-hexene 9.96% (11.83)

4/5 decene 9.12% (10.83)

1-decene 4.09% (4.86)

Decene fraction Major Acid Catalyst Product 5-methyl-1-nonene 32.14%(38.19)

3-propyl-1- heptene 14.59% (17.33)

4-ethyl-1-octene 13.13% (15.60)

2-butyl-1-hexene 9.96% (11.83)

4/5 decene 9.12% (10.83)

1-decene 4.09% (4.86)

In Table 2, the first column provides the name of the isomer, the GCarea % of that component in the feedstock from Table 1, and thenormalized amount of the isomer typically found in just the C₁₀ fractionof the feedstock. Table 2 also displays the structure of the mercaptansthat are produced from the C₁₀ olefin isomers. The second column showsthe structure of the major C₁₀ olefin isomers in the feedstock; thethird column displays the structure of the major mercaptan isomersproduced by a UV-initiated reaction with H₂S; and the fourth columndisplays the structure of the major mercaptan isomers produced by acidcatalysis.

A sample of the olefin feedstock was fractionated (e.g., distilled) andonly the C₁₀ fraction was isolated in high purity (e.g., a purifiedfeedstock). This product was submitted for H¹ and C¹³ NMR. The NMRanalysis (in mol %) was consistent with the information provided byGC-MS. The NMR confirmed that about 11 mol % of the total was vinylidene(2 butyl-1-hexene isomer) and about 11 mol % of the total purifiedfeedstock was internal olefins (linear decene isomers). The nomenclaturefor the various C₁₀ isomer products is shown in Table 3.

TABLE 3 Nomenclature for Mercaptan Reaction Products C₁₀ OlefinUV-initiated Mercaptans Acid-catalyzed Mercaptans 5-methyl- 5-methyl-1-5-methyl-2- 1-nonene mercapto-nonane mercapto-nonane 3-propyl-3-propyl-1- 3-propyl-2- 1-heptene mercapto-heptane mercapto-heptane4-ethyl- 4-ethyl-1- 4-ethyl- 1-octene mercapto-octane mercapto-octane2-butyl- 2-butyl-1- 5-mercapto-5- 1-hexene mercapto-hexane methyl-nonane4-decene 4-mercapto-decane 4-mercapto-decane 5-mercapto-decane5-mercapto-decane 5-decene 4-mercapto-decane 4-mercapto-decane5-mercapto-decane 5-mercapto-decane 1-decene 1-mercapto-decane2-mercapto-decane

Reaction of H₂S with the olefin feedstock (e.g., a feedstock comprisingbranched C₁₀ monoolefins) by UV initiation (e.g., using UV radiation)yielded mostly primary mercaptans, since the terminal olefin andvinylidene isomers yield predominately the anti-Markovnikov product. Theminor components were the secondary mercaptans from the terminal olefinand a tertiary mercaptan from the vinylidene isomer. Typically,UV-initiation of a terminal olefin produced primary mercaptans in 92-96area % range and secondary mercaptans in 4-8 area % range. The linearinternal olefin isomers present in the feedstock primarily producedsecondary mercaptan isomers. Thus, for the composition of the feedstockdisclosed herein, the distribution of mercaptans (i.e., the distributionwithin the C₁₀ fraction) in the resulting reaction product waspredominately primary mercaptans at about 80-90 area %. Secondarymercaptans were present at 10-20 area %, and tertiary mercaptans werepresent at about 0-3 area %. These ranges were calculated by NMRanalysis of the reaction product.

Reaction of H₂S with the olefin feedstock over an acid catalyst (such asFiltrol® 24 or Filtrol® 24X), produced as the major product theMarkovnikov product. Thus, the major mercaptan isomers containedsecondary mercaptans with some tertiary mercaptan. The relative ratio ofmercaptans was estimated at 85-90% secondary mercaptan and 10-15%tertiary mercaptan.

Reaction of H₂S with a feedstock comprising branched C₁₀ monoolefins inthe presence of a hydrodesulfurization (HDS) catalyst (such as HaldorTopsoe TK-554 or TK-570) produced mercaptans primarily similar indistribution to those produced by acid catalysis, which is theMarkovnikov distribution. However, the HDS catalyst also produces asignificant amount of the anti-Markovnikov product depending on theconditions used in the reaction step. Thus, under the conditionsevaluated for this disclosure, the product produced by the HDS catalystwas a blend of the product produced via acid catalysis with some of thecomponents produced by the UV-initiated reaction.

As will be appreciated by one of skill in the art, and with the help ofthis disclosure, the actual composition of the reaction product willultimately depend on a number of factors: the exact composition of thefeedstock, the ratio of H₂S to olefin that is used to produce thethiols, the catalytic method used to react the H₂S and olefin (UV vs.acid catalysis vs. HDS catalysis) to produce the product, etc. The finalproduct (e.g., any cuts separated from the crude to form, for example, acommercial product) will also depend on the purification step to removelights and whether a final product containing both mercaptan and sulfidefractions is desired or just one of the fractions, e.g., a mercaptanfraction or a sulfide fraction, is desired.

H₂S to Olefin Ratio:

The H₂S to olefin molar ratio is an important parameter in determiningthe amount of mercaptan and sulfide produced during the reaction step.This can be true regardless of the catalytic method employed. Withoutwishing to be limited by theory and in general, the higher the H₂S toolefin molar ratio, the greater the amount of mercaptans that will beproduced compared to the amount of sulfides produced.

A general reaction scheme for addition of H₂S to an olefin is shown inFIG. 1, regardless of catalytic method. For a C₁₀ olefin fraction, R, R′and R″ can be H or C₁-C₈ with the total of R+R′+R″=8. For 1-decene, Rand R′=H and R″=8 and can be a linear or branched alkyl group. For themajor isomers in a C₁₀ olefin fraction (e.g., a second feedstock asdisclosed herein), 5-methyl-1-nonene: R and R′=H and R″=8, but the alkylgroup contains branching at the 3^(rd) carbon atom of the C₈ fraction.

A sulfide fraction can be produced by further reaction of a mercaptanisomer with an olefin. The generic structures of such sulfides are shownin FIG. 1 and this fraction will consist of a variety of isomers withseveral possible combinations of sulfide structures depending on whetherthe sulfide is primary to primary, primary to secondary, primary totertiary, secondary to secondary, secondary to tertiary, or tertiary totertiary. The structures are complicated by the fact that on the twoportions of the sulfide the R, R′ and R″ value can be the same ordifferent depending on which mercaptan isomer reacts with which olefinisomer. The total number of carbon atoms of the two portions of thesulfide can also have different values for R+R′+R″, although the mostdominant combination will be where both sides each have a sum of 8 sincethe C₁₀ fraction predominates in the first feedstock and in the secondfeedstock.

Reaction Conditions:

Three different reaction methods were used to perform the reaction ofH₂S with a feedstock comprising branched C₁₀ monoolefins: UV initiation,acid catalysis, and HDS catalysis.

H₂S Removal:

In laboratory experimentation, H₂S was removed using a rotoevaporatorapparatus under conditions of reduced pressure. Under these conditions,H₂S was removed without removing significant quantities of lightcompounds.

Analytical Methods:

The weight percentage of thiol sulfur (wt. % SH) was determinedanalytically by titration using iodine in water as the titrant andmethylene chloride/isopropanol as the solvent system. Such titration canalso be done by using a silver nitrate titration method. Total sulfurwas measured by X-ray using a model SLFA-20 Horiba sulfur-in-oilanalyzer. GC analysis was performed using an Agilent Technologies 7890AGC. A 2m×0.25 mm×1.0 μm film DB-1 capillary column was used for theseparation. Operating conditions were as follows: 70° C. initialtemperature, 2 min hold time, 8° C./min ramp rate to 200° C. and then15° C./min ramp rate to 300° C. and hold for 10 minutes. A 2 ml/minhelium flow rate at constant flow conditions was used. A flameionization detector was used. The injector temperature was set at 275°C. and the detector temperature at 300° C. As described previously,these data from these compositions were reported in area %, which issubstantially similar and analogous to wt. %. Olefin conversion wasmonitored using Raman spectroscopy, with a Kaiser Optical System RXN24-channel spectrometer. The peak centered at 1640 cm⁻¹ was the vinylolefin, while the peak centered at about 1670 cm⁻¹ was the internalolefin.

UV Initiation:

Reactions were performed using either a 1.5 L or a 5-liter UV reactorequipped with a 100 watt lamp and ballast. The two reactors aresubstantially the same configuration, and the only difference inoperation is the amount of reactants added to the reactor. The reactionmixture was stirred at 500-1000 RPM. The reaction temperature wascontrolled with a bath set at 25° C., but the heat of reaction did reachabout 40° C. The lamp operated at 1.1-1.5 amps and 28-103 volts over thecourse of the reaction, operating at lower amps and higher voltage as itwarmed up. The reaction pressure was 220-280 psig (1,516 kPAg-1,930kPag) during the actual reaction time. Experiments were performed usingH₂S:olefin molar ratios of 1.0 and 10.2. The reaction was completed inabout 30 minutes based on the results of Raman Spectroscopy but wasallowed to continue for 60 minutes to ensure completion. FIGS. 2 and 4show typical gas chromatogram results of the UV-initiated crude reactionproduct, at H₂S:olefin mole ratios of 1:1 and 10.2:1, respectively,following removal of the H₂S (but prior to removal of any lights orother fractions).

Surprisingly and unexpectedly, after removing these samples from thereactor and venting off the residual H₂S using a rotoevaporator, theodor of this crude product was good. The limited odor of thesecompositions was an unexpected result that makes these compositionsadvantageous for use as mining collectors

Samples 1, 2, 3, and 4 were all prepared from crude reaction productsresulting from the UV-initiation process described in the precedingparagraphs.

Sample 1 (a comparative example) contained primarily C₁₀ n-decylmercaptans, low amounts of linear C₂₀ sulfides, and no branchedcompounds. Sample 1 was prepared from the crude reaction productresulting from the reaction of 1-decene with H₂S via the UV-initiatedreaction by distilling the crude product to remove H₂S and any lightfractions that were produced. Sample 2 contained mostly C₁₀ mercaptans(including branched C₁₀ mercaptans as described previously herein),prepared by first removing H₂S and the light fraction, and thendistilling the C₁₀ mercaptan fraction from the remaining intermediateand heavy crude reaction products to product a high purity C₁₀ mercaptanfraction. FIG. 7 shows a typical gas chromatogram analysis of thepurified C₁₀ mercaptan fraction obtained from the UV-initiated reactionproduct.

Sample 3 contained mostly C₂₀ sulfide compounds (including branched C₂₀sulfides as described previously herein) that were left behind after theH₂S, lights, and intermediates/mercaptans were distilled from the crudereaction product. Sample 4 contained mixed C₁₀ mercaptans and C₂₀sulfides (including branched C₁₀ mercaptans and branched C₂₀ sulfides asdescribed previously herein), prepared by distilling the crude reactionproduct to remove H₂S and the light fraction, which included (but is notlimited to) cyclohexane, ethylbenzene, 2-ethylhexanol and residualoctene, some decene isomers, and the majority of the octylmercaptan.FIGS. 3 and 5 show typical gas chromatogram results of the C₁₀mercaptan/C₂₀ sulfide reaction product obtained via the UV-initiatedreaction process and following the removal of the light fraction. Thedistillation process proceeded as follows: The first 7 fractions removedfrom the crude reaction product were considered to be the lightfractions. This distillation step was considered to be complete when thekettle temperature increased from 100° C. to 121° C. and the headtemperature increased from room temperature to 98.9° C. Cuts 8-13 wereconsidered to be the intermediate fractions and included the C₁₀mercaptans. These cuts were collected at a kettle temperature of 122° C.to 154° C. and a head temperature of 99° C. to 105° C. Cuts 14 and 15were collected at kettle and head temperatures of from 122° C. to 154°C. and 103.4° C. to 107.2° C., respectively. These cuts and whateverremained in the kettle were considered the heavies. The head temperaturewas allowed to increase from room temperature to 107.2° C. before thedistillation was stopped. For a typical distillation, only the lightfraction was distilled and the reaction product was what remained in thekettle after the lights were removed.

Acid Catalysis:

Acid catalyzed reactions produced a different distribution of isomerproducts than obtained by UV-initiation reaction of H₂S and the olefinfeedstock comprising branched C₁₀ monoolefins.

The product produced via the acid catalyzed addition of H₂S to thefeedstock comprising branched C₁₀ monoolefins was prepared in acontinuous flow reactor over Filtrol® 24 acid catalyst. The reactorcontained 43.22 g of catalyst and the WHSV (weight hourly spacevelocity) was maintained at 1.0 grams of olefin per gram of catalyst perhour. The H₂S to olefin molar ratio ranged from 10:1 to 1:1. Thereaction temperature was between 120° C. to 220° C., and the reactorpressure was 450-460 psig (3,100 kPa-3,200 kPa).

Acid catalysis produced the Markovnikov product. The vinyl components ofthe feedstock comprising branched C₁₀ monoolefins produced secondarymercaptans. The internal olefin components produced secondarymercaptans, while the vinylidene components produced tertiarymercaptans. Thus, the composition of the C₁₀ mercaptan fraction isomerswas different when compared to the composition of the product obtainedby UV-initiation. For example, the 5-methyl-1-nonene isomer produced5-methyl-2-mercapto-nonane via acid catalysis; and5-methyl-1-mercapto-nonane was the major product produced viaUV-initiation, with a minor amount of the 2-mercapto isomer as aby-product. The 2-butyl-1-hexene isomer produced5-methyl-5-mercapto-nonane via acid catalysis; while UV-initiationproduced 2-butyl-1-mercapto-hexane.

As with the product produced via UV-initiation, the product obtained byacid catalysis consisted of three general fractions after removal of theunwanted lights fraction. The C₁₀ mercaptan fraction comprised from50-100 wt. % of the crude kettle composition. The mercaptanfunctionality of the C₁₀ fraction was 85-95% secondary mercaptan and theremainder tertiary mercaptan. These isomers eluted in the 3.1-6.5 minuterange under the utilized GC conditions.

The intermediate fraction consisted of those mercaptan peaks in the6.5-14 minute range. However, the functionality of the mercaptans wassecondary and tertiary C₁₂ to C₁₈ mercaptans. The intermediate fractioncomprised 5-15% of the total kettle composition.

The sulfide fraction comprised 0-70% of the composition of the kettleproduct. The fraction consisted of sulfides primarily of formulaC₁₀H₂₁—S—C₁₀H₂₁. However, the isomer identity was different than thatfor the product produced via UV-initiation. The acid produced sulfideproduct was based on secondary and tertiary mercaptans rather thanpredominately primary mercaptans as in the UV-initiated producedproduct.

As with the samples produced via the UV-initiated process, theacid-catalyzed reaction products were subsequently further processed toremove H₂S and distill the crude reaction product into variousfractions.

Samples 5 and 6 were prepared from crude reaction product obtained viaacid catalysis. Sample 5 contained primarily mixed C₁₀ mercaptans andC₂₀ sulfides (including branched C₁₀ mercaptans and branched C₂₀sulfides as described previously herein), prepared by distilling thecrude reaction product as previously described to remove H₂S and lightfractions which included (but are not limited to) cyclohexane,ethylbenzene, 2-ethylhexanol and residual octene, some decene isomers,and the majority of the octylmercaptan. Sample 6 contained primarily C₂₀sulfide compounds (including branched C₂₀ sulfides as describedpreviously herein) that were left behind after the H₂S, lights, andintermediates/mercaptans, were distilled from the crude reactionproduct. FIG. 6 shows a typical gas chromatogram analysis of the C₁₀mercaptan/C₂₀ sulfide reaction product obtained via acid catalysisprocess and following the removal of the light fraction.

HDS Catalysis:

Reactions utilizing HDS catalysis produced mercaptans that wereprimarily similar in distribution to those produced by acid catalysis,which is the Markovnikov distribution. However, there was a tendency toalso produce some of the anti-Markovnikov distribution depending on thespecific conditions utilized in the reaction step. Thus the productproduced by the HDS catalyst appeared to be a blend of product producedprimarily via acid catalysis with some of the components of theUV-initiated reaction.

The HDS reaction conditions were as follows: WHSV was varied from 0.75to 2 grams of olefin per gram of catalyst per hour; the molar ratio ofH₂S per olefin was varied from 2:1 to 10:1; the average reactiontemperature was 180° C. to 220° C. The catalyst used was cobaltmolybdenum on alumina, examples being to Haldor Topsoe TK-554, TK-570,or similar. Olefin conversion, as determined by Raman Spectroscopy, wasin the 88-97 mol % range.

Under similar conditions of WHSV, ratio and temperature, the HDScatalyzed reaction produced more C₁₀ mercaptan fraction and less sulfidefraction than the acid catalyzed reaction. Comparison of the GC analysisof the crude reaction product produced from the HDS catalyzed reactionof H₂S and branched C₁₀ monoolefins showed that the HDS-catalyzedreaction produced a crude reaction product that was a blend of theproduct compositions produced by the UV-initiated and acid-catalyzedreactions. FIG. 8 shows a typical gas chromatogram analysis of the crudereaction product (with only H₂S removed) resulting from the HDScatalyzed reaction.

Recovery of Metals Using the Disclosed Sulfur-Containing Compounds inCollector Compositions

The recovery of metals using compositions comprising one or more of thebranched C₁₀ mercaptans and/or branched C₂₀ sulfides of the typedescribed as a collector composition was evaluated. The followingexamples include comparative examples which use mine standards for therecovery of metals, comparative examples which use Sample 1, andinventive examples which use Samples 2 to 6.

Four ore samples were obtained from four different mines, i.e., Ore 1from Mine 1, Ore 2 from Mine 2, Ore 3 from Mine 3, and Ore 4 from Mine4. These ore samples contained metal sulfide minerals from which themetal(s) (e.g., copper and/or molybdenum) can be recovered usingcollector compositions. Ore 1 can be characterized as containingchalcocite, chalcopyrite, and molybdenite minerals. Ore 2 can becharacterized as containing predominantly chalcocite and chalcopyriteminerals. Ore 3 can be characterized as containing chalcocite,chalcopyrite, and molybdenite minerals; however, is different incomposition and from a different mine than Ore 1. Ore 4 can becharacterized as containing predominantly chalcocite and chalcopyriteminerals; however, is different in composition and from a different minethan Ore 2.

The headgrade of each of the ores is summarized in Table 4 below.

TABLE 4 Ore Headgrade Summary Ore Cu Fe Mo S Total Insolubles 1 0.262.99 0.039 0.98 82.7 2 0.48 2.70 0.010 0.97 90.5 3 0.34 2.28 0.024 1.0391.5 4 0.42 2.28 0.009 1.59 77.7

Values are shown in wt. % based on the total weight of the ore forcopper, iron, molybdenum, sulfur, and total insolubles. Samples wereanalyzed for molybdenum content by digesting an ore sample over heat ina solution containing potassium chlorate, nitric acid, and hydrochloricacid. After the digested sample was cooled, super floc was added, andthe sample was analyzed via atomic absorption using a nitrousoxide-acetylene red flame. Standards ranged from 50-100 ppm by weightmolybdenum. A similar procedure with the necessary modifications wasused to analyze for copper and iron content.

Determination of Desired or Optimum Grind Time

Each of the metal recovery (e.g., flotation) procedures specified foreach of Ore 1, Ore 2, Ore 3, and Ore 4 required grinding the ore toprovide the ore samples at a specified particle size. The desiredparticle size was 30 wt. %+100 mesh solids (meaning 30% of the particlesare 149 microns or larger) for Ore 1; 25 wt. %+70 mesh solids (meaning25% of the particles are larger than 210 microns) for Ore 2; 36 wt.%+100 mesh solids (meaning 36% of the particles are 149 microns orlarger) for Ore 3; and 20 wt. %+100 mesh solids (meaning 20% of theparticles are 149 microns or larger) for Ore 4. The term “+100” refersto all particles collected on the 100 mesh screen and larger (e.g., 25,40, etc.). The term “+70” refers to all particles collected on the 70mesh screen and larger.

To determine the amount of time needed to provide the ores at thespecified particle size, referred to as the “desired grind time” or“optimum grind time,” an appropriate amount of ore from the appropriatemine (e.g., 900 to 1,000 grams, depending on the ore) was provided atthe −10 mesh size. This ore was placed in a rod mill with 20 lb of rodswith prescribed sizes (e.g., prescribed by the respective mine), and anappropriate amount of water (e.g., lime water) was added to give thedesired solids content. The rod mill was turned on for an amount of timebased on prior knowledge of that respective ore or an educated guessbased on experience with similar ore materials. After grinding for thedesired amount of time, the grind mixture was poured and rinsed with aminimum amount of tap water into a container. The water and solids werepoured through a 230 mesh wet screen sieve shaker while washing withwater to remove any fines. This was done in two batches to facilitatethe washing procedure. Failure to remove the fines often results in thematerial being glued together in chunks, analogous to concrete. Theremaining solids were removed from the screen with washing onto filterpaper in a Buchner funnel with vacuum. The solids collected were driedin an oven overnight at 75° C. The dried solids were then screenedthrough a series of screens (25 mesh, 40, 50, 70, 100, 140, 200, 230,and Pan) on a Ro-Tap® shaker in two batches, six minutes each. The abovegrind procedure was conducted at least three times to give a graph oftime vs. wt. % dry solids on a certain mesh screen size.

From the linear plot of this data, the “desired grind time” wasdetermined by adding the amount of solids on the screens up to thedesired mesh size for each ore. This procedure can be done periodically,but is necessary if the ore composition or the rod charge changes.

The desired grind time for Ore 1 was about 12 minutes, 18 seconds; thedesired grind time for Ore 2 was about 9 minutes, 0 seconds; the desiredgrind time for Ore 3 was about 5 minutes, 7 seconds; and the desiredgrind time for Ore 4 was about 13 minutes, 45 seconds.

Flotation Procedure for Ore 1 Using a Mine Standard as Example

The standard flotation procedure for Ore 1 is as follows. A 1-kg chargeof Ore 1 was added to a rod mill along with 650 mL tap water andapproximately 1 g of lime (this amount can be adjusted to obtain thedesired alkalinity, see above). The flotation collector reagents wereadded to the pool of water (not directly on the solids) in the millusing micro syringes: PAX (potassium amyl xanthate), 0.01 lb/metric ton@ 1% solution (1000 μL), made fresh daily; medium cycle oil (MCO), 0.05lb/metric ton, 24.6 μL; MC 37 collector (mixture of TDDM and MCO), 0.05lb/metric ton (26.1 μL); and plant frother (80% Nalco NALFLOTE® 9837/20%Cytec OREPREP® X-133), 28 μL. The mill was placed on rubber rollers andground for the predetermined time of 12 minutes, 18 seconds. The millwas removed from the rollers and the solids washed into a transparentplastic flotation cell (2.5 L). Only enough water was used to reach theflotation volume (2-liter mark on flotation cell). If too little waterwas used to wash the material into the flotation cell, additional limewater was added to reach the 2-liter flotation volume. The solids amountwas about 32 wt. % for Ore 1. The material was conditioned for two minat 1,200 rpm, then floated for five min at 1,200 rpm. Air was bubbledinto solution at the rate of 8 L/min. Froth was removed from the surfaceof the cell approximately every 10 sec with a plastic paddle. The frothwas collected in a glass pan under the lip of the cell. Liquid was addedperiodically to keep the solution near the lip of the cell so frothcould be easily removed. Care was taken to not have froth flow over thelip without raking with the paddle. The standpipe and back cell cornerswere washed down as needed with lime water. Depending on the frothinessof the ore, it can be necessary to restrict the air at the beginning ofthe flotation to prevent froth from overflowing the cell on its own.Generally, the air valve was completely open by the end of the firstminute. If not, then the amount of frother was adjusted. If it wasdifficult to maintain complete surface coverage with froth, a few moremicroliters of frothing agent were added. To do this, the air and timerwere shut off, and the froth concentrate was added and conditioned for30 seconds before turning back on the air and timer.

The air and stirring were turned off and the apparatus washed to removesolids from the stirrer and shaft into the flotation cell. Afterallowing the solids to settle for a few minutes, a sample was taken fortitration to determine alkalinity. The remaining tails were filteredthrough an 8-inch stainless steel filter (3 gallons) onto shark skinfilter paper. The collected solids were dried in an oven at 85° C.overnight to give dry solids that were weighed and labeled as tailings.

The rougher froth concentrate collected in the pan was filtered bywashing onto filter paper and dried in an oven at 85° C. overnight.Temperature was kept at/below 85° C. to prevent oxidation and weightchanges from occurring. The dried solids were weighed and labeled asconcentrate. Both the tailings and concentrate were analyzed fordetermination of copper, molybdenum, and iron.

The alkalinity titration procedure defined an alkalinity of 1.0 as beingequivalent to 0.01 lb of CaO per metric ton of solution. To prepare limewater of 30 alkalinity, 19 g of CaO were added to 50 L of water,agitated for at least one hour, then solids were settled overnight. Thelime water was decanted for use. For titration, to a 50 mL alkalinesolution, one drop of phenolphthalein indicator solution was added, andtitrated with 0.02N H₂SO₄ solution until the pink color disappeared.Each mL of titrating solution equaled 2.0 alkalinity units.

Assuming a solution is 30 alkalinity, that is, 0.3 lb CaO per metric tonof solution, then, (0.3 lb CaO/metric ton solution)*(metric ton/2000lb)*(8.345 lb/gal)*(gal/3.785 L)*(453.6 g/lb) converts to 0.15 g CaO/L,or 0.0075 g CaO/50 mL.

If the molecular weight of CaO=56 g/mol, and the molecular weight ofH₂SO₄=98 g/mol, and N=Molarity*net positive charge, then0.02N H₂SO₄=(0.02/2)*(98 g/mol)=(0.98 g/L)*(1 L/1000 mL)=0.00098 g/mL.

According to the stoichiometry of the reaction:CaO+H₂SO₄—CaSO₄+H₂O,

then 98 g H₂SO₄ neutralizes 56 g CaO.

If 0.0075 g CaO are present, then 0.0075×98/56=0.013125 gm H₂SO₄ arerequired, and 0.013125 g H₂SO₄/0.00098 g/mL=13.393 mL H₂SO₄.

Flotation Procedure for Ore 2 Using Mine Standard as Example

The standard flotation procedure for Ore 2 is as follows. The grind sizewas determined as described hereinabove. The optimum grind time was 9minutes. One kg bag of ore was charged and 650 mL of water was added tothe rod mill. The flotation procedure was carried out as described forthe Ore 1, except a time of 9 minutes was used. The standard collectorsystem for this ore was added to the grind: 14 μL of Cytec AERO® MX 7021and 12.5 μL of Cytec AERO® XD 5002—both of which are modifiedthionocarbamates. The frother added in the flotation cell was CytecOREPREP® X-133 at 5.6 μL dosage. The pH was adjusted to 11 with lime andthe mixer was started at 1,200 rpm for 1 min during the conditioningphase. The air was started and the froth was scraped for 6 min into onepan. The air was turned off and the final pH was checked. Theconcentrate and tailings materials were filtered, dried and weighed asdescribed for the Ore 1 procedure.

Flotation Procedure for Ore 3 Using a Mine Standard as Example

The standard flotation procedure for Ore 3 is as follows. The grind sizewas determined as described hereinabove. The optimum grind time was 5minutes, 7 seconds. A 900-g charge of ore, 0.6 g of lime, 32.5 μL ofdiesel, and 600 mL of water were charged into the rod mill. The optimumgrind time was utilized and the material transferred to the flotationcell as described above in the Ore 1 procedure. Then, 1,091 μL of a 1%solution of sodium ethyl xanthate and 28 μL of the 80/20 frothermentioned in the Ore 1 procedure were charged to the stirring liquid andconditioned for one min. The froth was collected for 3 min into acollection pan. The air was stopped and another 28 μL of frother and 546μL of 1% sodium ethyl xanthate were added to the slurry. The air wasrestarted and a 1-min conditioning phase was performed. The froth wasthen collected for another 2 min into the collection. The concentrateand tailings material were filtered, dried and weighed as described forthe Ore 1 procedure.

Flotation Procedure for Ore 4 Using a Mine Standard as Example

The standard flotation procedure for Ore 4 is as follows. The grind sizewas determined as described hereinabove, except the desired grind forOre 4 was 20% plus 100 mesh (meaning 20% of the particles are 149microns or larger). The optimum grind time to achieve these results was13.75 minutes. A 1-kg charge of ore was utilized. The amount of limeadded to the grind was 1.2 g along with 500 μL of thePAX/Dithiophosphate (DTP) 238 solution. The PAX/DTP 238 solution wasprepared by mixing 153 mL of distilled water with 0.5 mL DTP 238 and 0.5gram of PAX. The pH of the slurry was 10.5 after diluting with 650 mL ofwater and transferring to the flotation cell and diluting with water upto the 2-L mark. The slurry was stirred without air and 2000 μL ofPAX/DTP 238 solution were added along with 34 μL of a 50/50 vol. mixtureof pine oil/MIBC. The pulp was stirred at 1,200 rpm for one min and thenthe 8 L/min air was turned on. The froth was then raked over the weirfor 3 min into a pan. The air was turned off and an additional 34 μL ofpine oil/MIBC (frother) and 2000 μL of PAX/DTP were added followed byconditioning for 1 min. The air was then turned back on and the frothcollected for an additional 3 min into the pan. The air was then turnedoff while adding another 34 μL of pine oil/MIBC and 2,000 μL of PAX/DTPfollowed by conditioning for 1 min while stirring. The air was thenturned on for another min, followed by collecting the froth for 3 min.The air and stirring were then turned off and the concentrate pan wasremoved and the pulp mixture vacuum filtered to give the concentratethat was then dried in an oven overnight at 85° C. The tailings mixturewas then poured out into a filter with filter paper to obtain a wettailings mixture. This mixture was dried in an oven overnight at 85° C.The weight of the concentrate and tailings were recorded beforeanalytical analysis.

The mine standards for comparative examples C1 to C4 are shown in Table5 below:

TABLE 5 Summary of Mine Standards tested for Metals Recovery via OreFlotation Examples Mine Standard Cl lime, PAX, MCO, MC 37, and frotherC2 lime, thionocarbamate, and frother lime, sodium ethyl xanthatesolution, C3 diesel, and frother C4 lime, PAX/DTP 238, and frother

The flotation procedures above were used for Examples C1 to C4, with therecovery data shown below.

The mine standard for Ore 1 (per metric ton basis) contained 1200 g oflime, 1000 μL of 1% potassium amyl xanthate (PAX), 25 μL of medium cycleoil (MCO), 26 μL of MC 37 (mixture of TDDM and MCO), and 28 μL of plantfrother 80% Nalco NALFLOTE® 9837/20% Cytec OREPREP® X-133.

The mine standard for Ore 2 (per metric ton basis) contained 600 g oflime, 12.5 μL of thionocarbamate Cytec AERO® XD 5002, 14 μL ofthionocarbamate MX 7021, and 20 μL of frother Cytec AERO® X-133.

The mine standard for Ore 3 (per metric ton basis) contained 600 g oflime, 1637 μL of a 1% sodium ethyl xanthate solution in water, 32.5 μLof diesel, and 56 μL of pine oil/MIBC (frother).

The mine standard for Ore 4 (per metric ton basis) contained 1100 g oflime, 6500 μL of 1% PAX/DTP 238, and 102 μL of pine oil/MIBC (frother).

The flotation procedures above were performed for Comparative ExamplesC5 to C8 similarly to Comparative Examples C1 to C4. ComparativeExamples C5 to C8 substituted the sulfur-containing compounds of Sample1 for the respective combinations of PAX, MCO, MC 37, thionocarbamate,sodium ethyl xanthate solution, diesel, and PAX/DTP 238 contained in themine standards of C1 to C4.

Comparative Example C5 for Ore 1 used a collector composition containing1200 g of lime, Sample 1 in the amount specified in Table 8 below, and28 μL of plant frother 80% Nalco NALFLOTE® 9837/20% Cytec OREPREP®X-133.

Comparative Example C6 for Ore 2 used a collector composition containing600 g of lime, Sample 1 in the amount specified in Table 8 below, and 20μL of Cytec OREPREP® X-133 (frother).

Comparative Example C7 for Ore 3 used a collector composition containing600 g of lime, Sample 1 in the amount specified in Table 8 below, and 56μL of pine oil/MIBC (frother).

Comparative Example C8 for Ore 4 used a collector composition containing1100 g of lime, Sample 1 in the amount specified in Table 8 below, and102 μL of pine oil/MIBC (frother).

The sulfur-containing compounds used (i.e., Samples 2 to 6) in thecollector compositions for the inventive examples are shown in Table 6below:

TABLE 6 Summary of Sulfur-Containing Compounds Used in the CollectorCompositions Tested for Metals Recovery via Ore FlotationSulfur-Containing Method of Preparation Compounds in of the Sulfur-Examples the Collector Composition Containing Compounds 1 to 4 Sample 2:C₁₀ mercaptans UV-initiated catalysis of olefin feedstock 5 to 8 Sample3: C₂₀ sulfides UV-initiated catalysis of olefin feedstock  9 to 12Sample 4: mixed C₁₀ UV-initiated catalysis mercaptans-C₂₀ sulfides ofolefin feedstock 13 to 16 Sample 5: mixed C₁₀ Acid catalysis ofmercaptans C₂₀ sulfides olefin feedstock 17 to 20 Sample 6: C₂₀ sulfidesAcid catalysis of olefin feedstock

The flotation procedures above were performed for Examples 1 to 20similarly to Comparative Examples C1 to C4. Examples 1 to 20 substitutedsulfur-containing compounds comprising one of Samples 2 to 6 for therespective combination of PAX, MCO, MC 37, thionocarbamate, sodium ethylxanthate solution, diesel, and PAX/DTP 238 contained in the minestandards of C1 to C4.

Examples 1, 5, 9, 13, and 17 for Ore 1 used a collector compositioncontaining 1200 g of lime, one of Samples 2 to 6 in the amount specifiedin the Tables 7-13 below, and 28 μL of plant frother 80% Nalco NALFLOTE®9837/20% Cytec OREPREP® X-133.

Examples 2, 6, 10, 14, and 18 for Ore 2 used a collector compositioncontaining 600 g of lime, one of Samples 2 to 6 in the amount specifiedin Tables 7-13 below, and 20 μL of Cytec OREPREP® X-133 (frother).

Examples 3, 7, 11, 15, and 19 for Ore 3 used a collector compositioncontaining 600 g of lime, one of Samples 2 to 6 in the amount specifiedin Tables 7-13 below, and 56 μL of pine oil/MIBC (frother).

Examples 4, 8, 12, 16, and 20 for Ore 4 used a collector compositioncontaining 1100 g of lime, one of Samples 2 to 6 in the amount specifiedin Tables 7-13 below, and 102 μL of pine oil/MIBC (frother).

Tables 7 to 13 present data for Comparative Examples C1 to C8 andExamples 1 to 20 regarding the wt. % recoveries of copper, molybdenum,and iron from the four ores tested, using the standard chemicalcollectors for each ore, comparative sulfur-containing compounds ofSample 1, and the various mercaptan/sulfide compositions of Samples 2 to6, at different amounts. Duplicates of each flotation experiment wereconducted, and the average reported.

TABLE 7 Metals Recovery Using Mine Standards Comparative Recoveries %Grade % Example Ore Cu Mo Fe Cu Mo C1 1 91.2 92.8 24.4 9.7 1.37 C2 288.8 72.1 33.3 9.3 0.14 C3 3 92.8 93.7 38.7 4.8 0.34 C4 4 89.9 67.3 48.93.5 0.06

TABLE 8 Metals Recovery Using a C₁₀ n-Decyl Mercaptan-C₂₀ SulfideComposition Produced via UV Catalysis of 1-Decene Sulfur- Com- Con-parative taining Grade Ex- Com- Recoveries % % Dos- ample Ore pounds CuMo Fe Cu Mo age C5 1 Sample 1 91.1 93.0 12.5 9.7 1.48 15 μL C6 2 Sample1 85.7 68.2 27.9 7.1 0.12 25 μL C7 3 Sample 1 94.2 95.9 35.6 7.6 0.45 15μL C8 4 Sample 1 84.5 72.4 31.1 5.1  .07 15 μL

TABLE 9 Metals Recovery Using a C₁₀ Mercaptan Composition Produced viaUV Catalysis of the Olefin Feedstock Sulfur- Grade Ex- ContainingRecoveries % % Dos- ample Ore Compounds Cu Mo Fe Cu Mo age 1 1 Sample 291.1 87.0 13.1 8.7 1.42 15 μL 2 2 Sample 2 83.1 73.1 24.2 8.2 0.14 15 μL3 3 Sample 2 93.8 95.9 36.9 6.9 0.49 15 μL 4 4 Sample 2 85.2 66.5 28.45.6 0.09 15 μL

TABLE 10 Metals Recovery Using a C₂₀ Sulfide Composition Produced via UVCatalysis of the Olefin Feedstock Sulfur- Grade Containing Recoveries %% Example Ore Compounds Cu Mo Fe Cu Mo Dosage 5 1 Sample 3 91.8 94.811.7 10.5 1.62 15 μL 6 2 Sample 3 68.5 57.8 20.0  8.0 0.16 25 μL 7 3Sample 3 93.6 97.4 35.9  6.9 0.53 25 μL 8 4 Sample 3 84.9 70.1 26.1  5.30.10 15 μL

TABLE 11 Metals Recovery Using a Mixed C₁₀ Mercaptan-C₂₀ SulfideComposition Produced via UV Catalysis of the Olefin Feedstock Sulfur-Con- taining Ex- Com- Recoveries % Grade % Dos- ample Ore pounds Cu MoFe Cu Mo age  9 1 Sample 4 91.2 97.0 14.3 8.13 1.46 25 μL 10 2 Sample 482.1 68.5 25.9 8.59 0.14 25 μL 11 3 Sample 4 95.0 98.4 38.5 7.3  0.61 15μL 12 4 Sample 4 85.0 78.9 26.0 6.22 0.07  9 μL

TABLE 12 Metals Recovery Using a Mixed C₁₀ Mercaptan-C₂₀ SulfideComposition Produced via Acid Catalysis of the Olefin Feedstock Sulfur-Grade Containing Recoveries % % Example Ore Compounds Cu Mo Fe Cu MoDosage 13 1 Sample 5 92.4 95.1 14.5 8.35 1.14 15 μL 14 2 Sample 5 85.166.9 30.5 8.2  0.14 25 μL 15 3 Sample 5 93.9 98.4 40.0 6.1  0.43 25 μL16 4 Sample 5 82.7 61.8 40.6 5.25 0.10 25 μL

TABLE 13 Metals Recovery Using a C₂₀ Sulfide Composition Produced viaAcid Catalysis of the Olefin Feedstock Sulfur- Grade ContainingRecoveries % % Example Ore Compounds Cu Mo Fe Cu Mo Dosage 17 1 Sample 691.7 92.9 12.5 9.6 1.41 25 μL 18 2 Sample 6 69.9 71.3 21.3 8.2 0.17 25μL 19 3 Sample 6 94.4 96.1 37.2 6.5 0.49 15 μL 20 4 Sample 6 83.9 68.726.5 5.3 0.10 15 μL

As shown in Tables 7 to 13, and unexpectedly, the collector compositionsused in Examples 1 to 4 and 9 to 16 (containing mercaptan compositionsdisclosed herein) exhibited % recoveries of molybdenum of at least 60%,and in some cases, greater than 90%. In particular, the collectorcompositions described herein are capable of improving the molybdenumrecovery compared to that achieved using mine standards. As shown inTables 7-13, all of the compositions derived from the reaction of theolefin feedstock with H₂S resulted in the improved recovery ofmolybdenum from Ore 3 when used in a collector composition.Unexpectedly, molybdenum recovery ranged from 95.9% up to 98% with thesecompositions, compared to only 93.7% with the mine standards. Molybdenumrecovery was also improved compared to that achieved with the n-decylmercaptan composition that was produced via the UV-initiated reaction ofH₂S with 1-decene. Copper and iron recovery were comparable to thatachieved with the standard ore collectors.

Ore 1 also exhibited better molybdenum recoveries using all but one ofthe compositions derived from the olefin feedstock (87% to 97%) ascompared to both the mine standard collector (92.8%) and the n-decylmercaptan composition (93%). The recovery of copper from Ore 1 wascomparable to that of the mine standard. Similarly, specificcompositions (including the mixed C₁₀ mercaptans/C₂₀ sulfides producedvia UV initiation and the C₂₀ sulfides produced via UV initiation)improved the molybdenum recovery from Ore 4. Ore 2 did not exhibitimproved recovery of molybdenum with any of the compositions; however,it is not unexpected for the compositions to perform differently due tothe variability in the characteristics of these particular ores.

While not wishing to be limited by theory, the improvement in metalrecoveries observed, particularly in Ore 3, are hypothesized to be theresult of two possible effects. First, the level of branching in theseproducts is greater than the corresponding n-decyl product in Sample 1.The n-decyl product did not perform as well as the mixed C₁₀mercaptans/C₂₀ sulfides composition (Samples 4 and 5) in terms of copperrecovery (n-decyl 94.2% vs 95.0%) or molybdenum recovery (n-decyl 95.9%vs 98.4%). Secondly, comparison of the recoveries of the C₁₀ mercaptancomposition (Sample 2) with the mixed C₁₀ mercaptans/C₂₀ sulfidescomposition (Samples 4 and 5) which contains the sulfide heavies,demonstrates better recoveries of copper (95.0% vs. 93.8%) andmolybdenum (98.4% vs 95.9%) using the product containing the sulfideheavies. This suggests that both the branched compounds and sulfideheavies are responsible for the improved recovery/grade numbers. It isalso interesting to compare the C₂₀ sulfide composition (Sample 3, whichcontained 76.4% C₂₀) with that of the C₁₀ mercaptans/C₂₀ sulfidescomposition (Sample 4, which contained only 5.1% C₂₀ heavies). Note thatthe copper (95.0% vs. 93.6%) and molybdenum (98.4% vs. 97.4%) recoveriessuffered very little by such a dramatic increase in sulfide heavies. Twoconclusions can be drawn from these results. First, the sulfide heavyfraction is important to the activity of the reagent, as a more powerfulreagent is obtained by leaving the sulfide heavies in the product. Thesecond conclusion is that the level of sulfide heavies can bedramatically increased above what is typically produced in the crude(unpurified or undistilled) reaction mixture.

None of the compositions produced via the reaction of the olefinfeedstock with H₂S in the presence of the HDS catalyst were tested inthe metal recovery (“flotation”) procedures. However, because thecomposition of the crude reaction product produced using the HDScatalyst is essentially a blend of the compositions produced using aUV-initiator and an acid catalyst, it is expected that compositionsderived from the crude reaction product from the HDS-catalyzed reactionwould produce very similar results and trends to those observed for thecrude reaction products of UV-initiated and acid-catalyzed reactions. Inparticular, it is expected that Ores 1 and 3 would yield comparable orimproved recovery of molybdenum and copper if treated with either amixed C₁₀ mercaptan/C₂₀ sulfide composition, a C₁₀ mercaptancomposition, or a C₂₀ sulfide composition produced via HDS catalysis,and Ore 4 would yield comparable recoveries of molybdenum if treatedwith a mixed C₁₀ mercaptan/C₂₀ sulfide composition obtained via HDScatalysis.

ADDITIONAL DISCLOSURE

Accordingly, the scope of protection is not limited by the descriptionset out above but is only limited by the claims which follow, that scopeincluding all equivalents of the subject matter of the claims. Each andevery claim is incorporated into the specification as an embodiment ofthe present invention. Thus, the claims are a further description andare an addition to the detailed description of the present invention.The disclosures of all patents, patent applications, and publicationscited herein are hereby incorporated by reference.

Embodiment 1 is a process for the recovery of a metal from an ore. Theprocess comprises contacting the ore with a collector composition,wherein the collector composition comprises sulfur-containing compounds,wherein the sulfur-containing compounds comprise: (i) mercaptanscomprising branched C₁₀ mercaptans compounds selected from the groupconsisting of 5-methyl-1-mercapto-nonane, 3-propyl-1-mercapto-heptane,4-ethyl-1-mercapto-octane, 2-butyl-1-mercapto-hexane,5-methyl-2-mercapto-nonane, 3-propyl-2-mercapto-heptane,4-ethyl-2-mercapto-octane, 5-methyl-5-mercapto-nonane, and combinationsthereof; and (ii) sulfides comprising branched C₂₀ sulfides representedby the structure R¹—S—R², wherein R¹ and R² are each independently afunctional group derived from an olefin, wherein the olefin comprises5-methyl-1-nonene, 3-propyl-1-heptene, 4-ethyl-1-octene,2-butyl-1-hexene, or combinations thereof.

Embodiment 2 is the process of embodiment 1, wherein the step ofcontacting is performed at least once during a metal flotationprocedure.

Embodiment 3 is the process of any of embodiments 1 to 2, wherein thesulfur-containing compounds are present in an amount of less than 0.1wt. % based on a combined total weight of the collector composition andthe ore.

Embodiment 4 is the process of any of embodiments 1 to 3, whereinsulfur-containing compounds comprise from about 15 wt. % sulfides toabout 80 wt. % sulfides, and wherein the sulfides are the branched C₂₀sulfides.

Embodiment 5 is the process of any of embodiments 1 to 4, wherein thecollector composition further comprises water, a pH control agent, afrothing agent, a hydrocarbon, an oily reagent, a water immiscibleliquid, or combinations thereof.

Embodiment 6 is the process of any of embodiments 1 to 5, wherein thebranched C₁₀ mercaptans are present in an amount of at least about 50wt. % based on a total weight of the mercaptans in the collectorcomposition.

Embodiment 7 is the process of any of embodiments 1 to 6, wherein thebranched C₂₀ sulfides are present in an amount of at least 50 wt. %based on a total weight of the sulfides in the collector composition.

Embodiment 8 is the process of any of embodiments 1 to 7, wherein themetal comprises gold, silver, platinum, copper, nickel, iron, lead,zinc, molybdenum, cobalt, chromium, or combinations thereof.

Embodiment 9 is the process of any of embodiments 1 to 8, wherein themetal comprises copper, and a percent recovery of copper from the ore isat least 85 wt. %.

Embodiment 10 is the process of any of embodiments 1 to 9, wherein themetal comprises molybdenum, and a percent recovery of molybdenum fromthe ore is at least 75 wt. %.

Embodiment 11 is the process of any of embodiments 1 to 10, whereinduring the step of contacting, the sulfur-containing compounds arepresent in a range from about 4.5 grams to about 50 grams per metric tonof ore.

Embodiment 12 is the process of any of embodiments 1 to 11, wherein theore is in the form of ore particles in the step of contacting.

Embodiment 13 is the process of any of embodiments 1 to 12, wherein theore comprises a copper-bearing ore, a molybdenum-bearing ore, or both acopper-bearing ore and a molybdenum-bearing ore.

Embodiment 14 is a collector composition comprising sulfur-containingcompounds, the sulfur-containing compounds comprising (i) mercaptanscomprising branched C₁₀ mercaptans compounds selected from the groupconsisting of 5-methyl-1-mercapto-nonane, 3-propyl-1-mercapto-heptane,4-ethyl-1-mercapto-octane, 2-butyl-1-mercapto-hexane,5-methyl-2-mercapto-nonane, 3-propyl-2-mercapto-heptane,4-ethyl-2-mercapto-octane, 5-methyl-5-mercapto-nonane, and combinationsthereof; and (ii) sulfides comprising branched C₂₀ sulfides representedby the structure R¹—S—R², wherein R¹ and R² are each independently afunctional group derived from an olefin, wherein the olefin comprises5-methyl-1-nonene, 3-propyl-1-heptene, 4-ethyl-1-octene,2-butyl-1-hexene, or combinations thereof.

Embodiment 15 is the collector composition of embodiment 14, wherein thesulfur-containing compounds are present in an amount of less than 0.1wt. % based on a combined total weight of the collector composition andthe ore.

Embodiment 16 is the collector composition of any of embodiments 14 to15, wherein the sulfur-containing compounds comprise from about 15 wt. %to about 80 wt. % sulfides, and wherein the sulfides are the branchedC₂₀ sulfides.

Embodiment 17 is the collector composition of any of embodiments 14 to16, wherein the branched C₁₀ mercaptans are present in an amount of atleast about 50 wt. % based on a total weight of the mercaptans in thecollector composition.

Embodiment 18 is the collector composition of any of embodiments 14 to17, wherein the branched C₂₀ sulfides are present in an amount of atleast 50 wt. % based on a total weight of the sulfides in the collectorcomposition.

Embodiment 19 is the collector composition of any of embodiments 14 to18, further comprising water, a pH control agent, a frothing agent, ahydrocarbon, an oily reagent, a water immiscible liquid, or combinationsthereof.

Embodiment 20 is the collector composition of any of embodiments 14 to19, further comprising a second collector agent.

Embodiment 21 is the collector composition of embodiment 20, wherein thesecond collector agent is xanthate, a xanthic ester, a thionocarbonate,a dialkyl dithiophosphate, or combinations thereof.

Embodiment 22 is the collector composition of any of embodiments 14 to21, wherein the sulfur-containing compounds of the collector compositionhave an odor which is less unpleasant than an odor of mercaptancompounds which are n-decyl mercaptans, n-dodecyl mercaptans,tert-dodecyl mercaptans, or combinations thereof present in an amount ofequal to or greater than about 25 wt. % of the mercaptan compounds in anotherwise similar mining collector composition.

Embodiment 23 is the process of any of embodiments 1 to 13, wherein thesulfur-containing compounds of the collector composition have an odorwhich is less unpleasant than an odor of mercaptan compounds which aren-decyl mercaptans, n-dodecyl mercaptans, tert-dodecyl mercaptans, orcombinations thereof present in an amount of equal to or greater thanabout 25 wt. % of the mercaptan compounds in an otherwise similar miningcollector composition.

Embodiment 24 is the process of any of embodiments 1 to 13 and 23,wherein the collector composition further comprises a second collectoragent.

Embodiment 25 is the process of any of embodiments 23 to 24, wherein thesecond collector agent is xanthate, a xanthic ester, a thionocarbonate,a dialkyl dithiophosphate, or combinations thereof.

While embodiments of the disclosure have been shown and described,modifications thereof can be made without departing from the spirit andteachings of the invention. The embodiments and examples describedherein are exemplary only, and are not intended to be limiting. Manyvariations and modifications of the invention disclosed herein arepossible and are within the scope of the invention.

At least one embodiment is disclosed and variations, combinations,and/or modifications of the embodiment(s) and/or features of theembodiment(s) made by a person having ordinary skill in the art arewithin the scope of the disclosure. Alternative embodiments that resultfrom combining, integrating, and/or omitting features of theembodiment(s) are also within the scope of the disclosure. Wherenumerical ranges or limitations are expressly stated, such expressranges or limitations should be understood to include iterative rangesor limitations of like magnitude falling within the expressly statedranges or limitations (e.g., from about 1 to about 10 includes, 2, 3, 4,etc.; greater than 0.10 includes 0.11, 0.12, 0.13, etc.). For example,whenever a numerical range with a lower limit, R_(l), and an upperlimit, R_(u), is disclosed, any number falling within the range isspecifically disclosed. In particular, the following numbers within therange are specifically disclosed: R=R_(l)+k*(R_(u)−R_(l)), wherein k isa variable ranging from 1 percent to 100 percent with a 1 percentincrement, i.e., k is 1 percent, 2 percent, 3 percent, 4 percent, 5percent, . . . 50 percent, 51 percent, 52 percent . . . 95 percent, 96percent, 97 percent, 98 percent, 99 percent, or 100 percent. Moreover,any numerical range defined by two R numbers as defined in the above isalso specifically disclosed. Use of the term “optionally” with respectto any element of a claim means that the element is required, oralternatively, the element is not required, both alternatives beingwithin the scope of the claim. Use of broader terms such as comprises,includes, and having should be understood to provide support fornarrower terms such as consisting of, consisting essentially of, andcomprised substantially of.

Accordingly, the scope of protection is not limited by the descriptionset out above but is only limited by the claims which follow, that scopeincluding all equivalents of the subject matter of the claims. Each andevery claim is incorporated into the specification as an embodiment ofthe present invention. Thus, the claims are a further description andare an addition to the detailed description of the present invention.The disclosures of all patents, patent applications, and publicationscited herein are hereby incorporated by reference.

What is claimed is:
 1. A process for the recovery of a metal from anore, the process comprising: contacting the ore with a collectorcomposition, wherein the collector composition comprisessulfur-containing compounds, wherein the sulfur-containing compoundscomprise; (i) mercaptans comprising branched C₁₀ mercaptans compoundsselected from the group consisting of 5-methyl-1-mercapto-nonane,3-propyl-1-mercapto-heptane, 4-ethyl-1-mercapto-octane,2-butyl-1-mercapto-1-hexane, 5-methyl-2-mercapto-nonane,3-propyl-2-mercapto-heptane, 4-ethyl-2-mercapto-octane,5-methyl-5-mercapto-nonane, and combinations thereof; and (ii) sulfidescomprising branched C₂₀ sulfides represented by the structure R¹—S—R²,wherein R¹ and R² are each independently a functional group derived froman olefin, wherein the olefin comprises 5-methyl-1-nonene,3-propyl-1-heptene, 4-ethyl-1-octene, 2-butyl-1-hexene, or combinationsthereof.
 2. The process of claim 1, wherein the step of contacting isperformed at least once during a metal flotation procedure.
 3. Theprocess of claim 1, wherein the sulfur-containing compounds are presentin an amount of less than 0.1 wt. % based on a combined total weight ofthe collector composition and the ore.
 4. The process of claim 1,wherein sulfur-containing compounds comprise from about 15 wt. %sulfides to about 80 wt. % sulfides, and wherein the sulfides are thebranched C₂₀ sulfides.
 5. The process of claim 1, wherein the collectorcomposition further comprises water, a pH control agent, a frothingagent, a hydrocarbon, an oily reagent, a water immiscible liquid, orcombinations thereof.
 6. The process of claim 1, wherein the branchedC₁₀ mercaptans are present in an amount of at least about 50 wt. % basedon a total weight of the mercaptans in the collector composition.
 7. Theprocess of claim 1, wherein the branched C₂₀ sulfides are present in anamount of at least 50 wt % based on a total weight of the sulfides inthe collector composition.
 8. The process of claim 1, wherein the metalcomprises gold, silver, platinum, copper, nickel, iron, lead, zinc,molybdenum, cobalt, chromium, or combinations thereof.
 9. The process ofclaim 1, wherein the metal comprises copper, and a percent recovery ofcopper from the ore is at least 85 wt. %.
 10. The process of claim 1,wherein the metal comprises molybdenum, and a percent recovery ofmolybdenum from the ore is at least 75 wt. %.
 11. The process of claim1, wherein during the step of contacting, the sulfur-containingcompounds are present in a range from about 4.5 grams to about 50 gramsper metric ton of ore.
 12. The process of claim 1, wherein the ore is inthe form of ore particles in the step of contacting.
 13. The process ofclaim 1, wherein the ore comprises a copper-bearing ore, amolybdenum-bearing ore, or both a copper bearing ore and amolybdenum-bearing ore.
 14. The process of claim 2, wherein thesulfur-containing compounds are present in an amount of less than 0.1wt. % based on a combined total weight of the collector composition andthe ore.
 15. The process of claim 14, wherein the sulfur-containingcompounds comprise from about 15 wt. % to about 80 wt. % sulfides, andwherein the sulfides are the branched C₂₀ sulfides.
 16. The process ofclaim 15, wherein the branched C₁₀ mercaptans are present in an amountof at least about 50 wt. % based on a total weight of the mercaptans inthe collector composition.
 17. The process of claim 16, wherein thebranched C₂₀ sulfides are present in an amount of at least 50 wt. %based on a total weight of the sulfides in the collector composition.18. The process of claim 17, wherein the collector composition furthercomprises water, a pH control agent, a frothing agent, a hydrocarbon, anoily reagent, a water immiscible liquid, or combinations thereof. 19.The process of claim 1, wherein the collector composition furthercomprises a second collector agent.
 20. The process of claim 19, whereinthe second collector agent is xanthate, a xanthic ester, athionocarbonate, dialkyl dithiophosphate, or combinations thereof. 21.The process of claim 1, wherein the sulfur-containing compounds of thecollector composition have an odor which is less unpleasant than an odorof mercaptan compounds which are n-decyl mercaptans, n-dodecylmercaptans, tert-dodecyl mercaptans, or combinations thereof present inan amount of equal to or greater than about 25 wt. % of the mercaptancompounds in an otherwise similar mining collector composition.
 22. Theprocess of claim 17, wherein the sulfur-containing compounds of thecollector composition have an odor which is less unpleasant than an odorof mercaptan compounds which are n-decyl mercaptans, n-dodecylmercaptans, tert-dodecyl mercaptans, or combinations thereof present inan amount of equal to or greater than about 25 wt. % of the mercaptancompounds in an otherwise similar mining collector composition.